CN113786845B - Preparation method for synthesizing multi-component iron-based nanocomposite material with assistance of carbon dots - Google Patents
Preparation method for synthesizing multi-component iron-based nanocomposite material with assistance of carbon dots Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims description 16
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 229940072172 tetracycline antibiotic Drugs 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- -1 iron ions Chemical class 0.000 abstract description 2
- 238000006557 surface reaction Methods 0.000 abstract 1
- 239000004098 Tetracycline Substances 0.000 description 12
- 235000019364 tetracycline Nutrition 0.000 description 12
- 229960002180 tetracycline Drugs 0.000 description 9
- 229930101283 tetracycline Natural products 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 7
- 150000003522 tetracyclines Chemical class 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011294 coal tar pitch Substances 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229940040944 tetracyclines Drugs 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 241000186361 Actinobacteria <class> Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002424 anti-apoptotic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000000324 neuroprotective effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of a carbon-point-assisted synthesized multi-component iron-based nanocomposite, which takes CDs as a strong platform, and carries out various chemical reactions with specific precursors/additives at the same time, and by virtue of the surface reaction activity of the CDs, CDs mainly convert iron ions into zero-valent iron at high temperature, and meanwhile, the zero-valent iron reacts with sulfate radicals and ammonia gas to form a new phase structure. In the preparation method of the multi-component iron-based nanocomposite synthesized by the carbon point assistance, all chemical reactions and nucleation processes are limited on the surface of CDs, so that the growth and agglomeration of crystal nuclei among CDs can be effectively inhibited, and the obtained multi-component iron-based nanocomposite can activate H simultaneously 2 O 2 And PS, can effectively degrade tetracycline antibiotics dyes without any energy consumption.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a preparation method for synthesizing a multi-component iron-based nanocomposite material with the assistance of carbon points.
Background
Nanocomposite combining two or more different components on one nanosystem represents a bottom-up design strategy for designing advanced structures with better performance and multi-functional integration. Such properties result from the fusion of different materials. Although a variety of nanocomposite materials have been synthesized, the combination and synergistic effects of which have been demonstrated in terms of their optical, electronic and catalytic properties, the preparation of hybrid materials with multicomponent as well as controlled morphology dimensions remains a difficulty and hotspot of current research.
As a non-toxic element quantum dot, carbon Dots (CDs) are increasingly attracting attention in the fields of bioimaging, drug delivery, sensors, functional materials, pollutant degradation, catalysis, etc., and the increasing popularity of carbon dots can also be verified by their rapid, simple and inexpensive synthetic routes, scalability in mass production, and adjustable surface structures. In general, CDs consist of a graphite core surrounded by oxygen-containing and/or nitrogen-containing groups, which imparts unique chemical behaviors to the surrounding environment, including recognition/binding, reactivity, redox, and the like. For example, specific CDs are used to design probes to sensitively and selectively detect various metal ions, such as Fe, by virtue of their different affinities for the surface active groups of the CDs 2+/3+ ，Cu 2+ ，Hg 2 + ，Pb 2+ Etc. These metal ions typically cause changes in CDs fluorescence through surface adsorption and electron/energy transfer. In addition, the electron donor capability of CDs allows them to reduce noble metals or copper salts to elemental metals under light irradiation or hydrothermal reaction conditions. Thus, CDs appear as coupled components that cooperate to build hybrid nanostructures with properties that exceed those of individual components. And CDs can be spliced into two-dimensional (2D) carbon nano sheets through surface group reaction at high temperature, so that growth and aggregation of surface formation crystal nuclei in other directions are effectively prevented. By this method, various carbon-based hybrid materials are expected to be designed into novel structures having excellent stability and activity. In addition to the basic role as heterogeneous nucleants and carriers, the reactivity of CDs may also promote the formation of multiple components of the nanocomposite to promote its catalytic properties.
Disclosure of Invention
In order to further improve the catalytic performance of the nanocomposite, the invention adopts the following technical scheme:
the preparation method for synthesizing the multi-component iron-based nanocomposite material by assisting carbon points comprises the following steps:
step 1, adding 0.1-0.15 g of carbon dot powder and 0.2224-0.3336 g of ferrous sulfate into 20mL of deionized water, and performing ultrasonic dispersion for 0.5-1 h at 25-35 ℃ and a frequency of 20-30 KHz to obtain a carbon dot-ferrous sulfate mixed solution;
step 2, adding 20-40 mL of ammonia water with volume concentration of 25v/v% into the carbon dot-ferrous sulfate mixed solution obtained in the step 1, performing ultrasonic dispersion for 0.5-1 h at the temperature of 25-35 ℃ and the frequency of 20-30 KHz, then placing the mixed solution after ultrasonic dispersion into an electrothermal blowing drying box, and drying at the temperature of 70-90 ℃ to obtain dark brown solid;
step 3, fully grinding the dark brown solid obtained in the step 2 in a mortar for 0.25-0.5 h to obtain dark brown powder;
and 4, placing the dark brown powder obtained by grinding in the step 3 into a tube furnace, calcining for 2-4 hours at 700-900 ℃ under the protection of argon, wherein the heating rate of the tube furnace is 5-10 ℃/min, the argon flow is 20-40 sccm, and then naturally cooling the tube furnace to room temperature to finally obtain the multi-component iron-based nanocomposite.
The CDs powder is obtained by selectively etching coal tar pitch by formic acid and hydrogen peroxide according to the method for preparing multicolor luminous adjustable carbon dots by using coal tar pitch disclosed in patent ZL 201610534465.4.
The ferrous sulfate is replaced by nickel sulfate salt and cobalt sulfate salt, so that the preparation of the multi-component nickel-based, cobalt-based and other nanocomposite materials can be realized.
The ferrous sulfate may be replaced with ferric sulfate.
In the preparation method of the multi-component iron-based nanocomposite synthesized by carbon dots in an auxiliary way, all chemical reactions and nucleation processes are limited on the surfaces of CDs, so that the growth and agglomeration of crystal nuclei among CDs can be effectively inhibited, and the obtained multi-component iron-based nanocomposite can simultaneously activate H 2 O 2 And PS, can effectively degrade tetracycline antibiotics dyes without any energy consumption.
Drawings
FIG. 1 is an X-ray diffraction pattern of a synthetic multicomponent iron-based nanocomposite of the present invention;
FIG. 2 is a Raman spectrum of a synthetic multicomponent iron-based nanocomposite of the present invention;
FIG. 3 is a high resolution transmission electron micrograph of a synthetic multicomponent iron-based nanocomposite of the present invention;
FIG. 4 is a high resolution transmission electron micrograph of a synthetic multicomponent iron-based nanocomposite of the present invention;
FIG. 5 is a schematic diagram of a synthetic multicomponent iron-based nanocomposite N according to the invention 2 Adsorption-desorption isotherms;
FIG. 6 shows the synthesis of multicomponent iron-based nanocomposite activated H according to the invention 2 O 2 Graph of reaction rate for degradation of Tetracycline (TC).
FIG. 7 is an illustration of the activation of PS and H by the synthetic multicomponent iron-based nanocomposite of the invention 2 O 2 Reaction rate diagram of +ps degradation of Tetracycline (TC).
Detailed Description
The following describes the detailed technical scheme of the invention with reference to the accompanying drawings:
the preparation method for synthesizing the multi-component iron-based nanocomposite material by assisting carbon points comprises the following steps:
step 1, adding 0.1-0.15 g of carbon dot powder and 0.2224-0.3336 g of ferrous sulfate into 20mL of deionized water, and performing ultrasonic dispersion for 0.5-1 h at 25-35 ℃ and a frequency of 20-30 KHz to obtain a carbon dot-ferrous sulfate mixed solution;
step 2, adding 20-40 mL of ammonia water with volume concentration of 25v/v% into the carbon dot-ferrous sulfate mixed solution obtained in the step 1, performing ultrasonic dispersion for 0.5-1 h at the temperature of 25-35 ℃ and the frequency of 20-30 KHz, then placing the mixed solution after ultrasonic dispersion into an electrothermal blowing drying box, and drying at the temperature of 70-90 ℃ to obtain dark brown solid;
step 3, fully grinding the dark brown solid obtained in the step 2 in a mortar for 0.25-0.5 h to obtain dark brown powder;
and 4, placing the dark brown powder obtained by grinding in the step 3 into a tube furnace, calcining for 2-4 hours at 700-900 ℃ under the protection of argon, wherein the heating rate of the tube furnace is 5-10 ℃/min, the argon flow is 20-40 sccm, and then naturally cooling the tube furnace to room temperature to finally obtain the multi-component iron-based nanocomposite.
The CDs powder is obtained by selectively etching coal tar pitch by formic acid and hydrogen peroxide according to the method for preparing multicolor luminous adjustable carbon dots by using coal tar pitch disclosed in patent ZL 201610534465.4.
The ferrous sulfate is replaced by nickel sulfate salt and cobalt sulfate salt, so that the preparation of the multi-component nickel-based, cobalt-based and other nanocomposite materials can be realized.
The ferrous sulfate may be replaced with ferric sulfate.
Example 1
The preparation method for synthesizing the multi-component iron-based nanocomposite material by assisting carbon points comprises the following steps:
step 1 0.1g of carbon point powder and 0.26g of ferrous sulfate (FeSO 4 ·7H 2 O) adding the mixture into 20mL of deionized water, and performing ultrasonic dispersion for 1h at the temperature of 30 ℃ and the frequency of 30KHz to obtain a carbon dot-ferrous sulfate mixed solution;
step 2, adding 30mL of ammonia water with the volume concentration of 25v/v% into the carbon dot-ferrous sulfate mixed solution obtained in the step 1, performing ultrasonic dispersion for 1h at the temperature of 30 ℃ and the frequency of 30KHz, then placing the mixed solution after ultrasonic dispersion into an electrothermal blowing drying oven, and drying at the temperature of 90 ℃ to obtain dark brown solid;
step 3, fully grinding the black solid obtained in the step 2 in a mortar for 0.5h to obtain dark brown powder;
and 4, placing the dark brown powder obtained by grinding in the step 3 into a tube furnace, calcining for 2 hours at 900 ℃ under the protection of argon, wherein the heating rate of the tube furnace is 5 ℃/min, the argon flow is 20sccm, and naturally cooling the tube furnace to room temperature to finally obtain the multi-component iron-based nanocomposite. The multicomponent iron-based nanocomposite obtained in the examples was characterized and tested for X-ray diffraction patterns, as shown in fig. 1, which shows diffraction peaks at 30.0 °, 33.9 °, 43.9 ° and 53.3 ° 2θ with Fe 7 S 8 (JCPDS No. 76-2308) corresponds to the simple substance Fe (JCPDS No. 87-0721), and two diffraction peaks at 44.7 DEG and 65.0 DEG correspond to FeN, and diffraction peaks at 43.6 DEG, 50.8 DEG and 74.6 DEG correspond to FeN 0.0324 (JCPDS No. 75-2127) phase;
the Raman spectrum of the multicomponent iron-based nanocomposite obtained in the test example, as shown in FIG. 2, is FeNS@PC at 1336 and 1580cm -1 Two broader and weaker peaks were observed, indicating that porosity in the sample resulted in a poorer degree of graphitization;
a high-resolution transmission electron micrograph of the multi-component iron-based nanocomposite prepared in the embodiment is shown in FIG. 3, the center of the black core-shell structure is elemental iron, and the surrounding coating layer is Fe 7 S 8 And FeN 0.0324 ；
The high resolution transmission electron micrographs of the multicomponent iron-based nanocomposite obtained in the examples are shown in FIG. 4, and the distances between the different lattice fringes are 0.14nm, 0.26nm and 0.21nm, respectively corresponding to the (200) interplanar spacings of Fe, by measurement 7 S 8 (203) interplanar spacing and FeN 0.0324 (111) Interplanar spacing;
n of the multicomponent iron-based nanocomposite obtained in the examples 2 The adsorption-desorption isothermal curve is shown in FIG. 5, which shows that the specific surface area of the sample reaches 209.39m 2 And/g, indicating that the porous carbon structure is formed, and has excellent adsorption capacity for pollutants;
tetracyclines are a broad-spectrum antibiotic produced by actinomycetes and have been widely used worldwide because of their low cost and excellent anti-inflammatory, anti-apoptotic and neuroprotective effects. The undegraded tetracycline wastewater is discharged into the environment, which causes great pollution to the environmental water body. Multicomponent carbon-based composite nanomaterials can be produced by activating hydrogen peroxide (H 2 O 2 ) Or sodium Persulfate (PS) generates hydroxyl radicals and sulfate radicals to degrade Tetracycline (TC) antibiotics. However, the H can be activated simultaneously under different pH conditions 2 O 2 And PS degradation of tetracycline antibiotics have been reported.
The multicomponent iron-based nanocomposite obtained in the examples was used for the degradation of Tetracyclines (TC), which activates H 2 O 2 Degradation of Tetracyclines (TC) and activation of PS and H 2 O 2 The reaction rate diagrams of +PS are shown in FIGS. 6 and 7, respectively. The degradation experiment shows that CDs can be used as aAnd a strong platform is used for carrying out various chemical reactions with specific precursors/additives, CDs are subjected to the transformation of main iron ions to zero-valent iron at high temperature by virtue of the surface reactivity of the precursor/additive, and meanwhile, the zero-valent iron reacts with sulfate and ammonia to form a new phase structure. All chemical reactions and nucleation processes are limited to the surface of CDs, and the growth and agglomeration of crystal nuclei among CDs are effectively inhibited. Thus, the multicomponent iron-based nanocomposite material prepared in the examples had elemental iron as the core, surrounded by Fe 7 S 8 And FeN x Component shell, the obtained multicomponent iron-based nanocomposite material can activate H simultaneously 2 O 2 And PS, effectively degrade tetracycline antibiotics dyes, and do not need any energy consumption.
Claims (2)
1. The preparation method for synthesizing the multi-component iron-based nanocomposite material with the assistance of carbon points is characterized by comprising the following steps of: the method comprises the following steps:
step 1, adding 0.1-0.15 g carbon point powder and 0.2224-0.3336 g ferrous sulfate into 20mL deionized water, and performing ultrasonic dispersion at 25-35 ℃ and frequency of 20-30 KHz for 0.5-1 h to obtain a carbon point-ferrous sulfate mixed solution;
step 2, adding 20-40 mL volume percent of ammonia water with the concentration of 25-v/v% into the carbon dot-ferrous sulfate mixed solution obtained in the step 1, performing ultrasonic dispersion on the mixed solution at the temperature of 25-35 ℃ and the frequency of 20-30 KHz for 0.5-1 h, then placing the mixed solution after ultrasonic dispersion into an electrothermal blowing drying box, and drying the mixed solution at the temperature of 70-90 ℃ to obtain dark brown solid;
step 3, fully grinding the dark brown solid obtained in the step 2 in a mortar for 0.25-0.5-h to obtain dark brown powder;
and 4, placing the dark brown powder obtained by grinding in the step 3 into a tube furnace, calcining the dark brown powder at 700-900 ℃ under the protection of argon, wherein the heating rate of the tube furnace is 5-10 ℃/min, the argon flow is 20-40 sccm, and naturally cooling the tube furnace to room temperature to finally obtain the multi-component iron-based nanocomposite.
2. The method for preparing the carbon-point-assisted synthesized multi-component iron-based nanocomposite according to claim 1, wherein the method comprises the following steps: the ferrous sulfate may be replaced with ferric sulfate.
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