CN112808272B - Nano composite substrate with SERS activity and degradation performance and preparation method thereof - Google Patents

Nano composite substrate with SERS activity and degradation performance and preparation method thereof Download PDF

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CN112808272B
CN112808272B CN202011536464.6A CN202011536464A CN112808272B CN 112808272 B CN112808272 B CN 112808272B CN 202011536464 A CN202011536464 A CN 202011536464A CN 112808272 B CN112808272 B CN 112808272B
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mgo
gold nanoparticles
washing
suspension
solution
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CN112808272A (en
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渠陆陆
田菲
杨国海
张迎娣
戴诗雨
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Jiangsu Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

A method of preparing a nanocomposite substrate having SERS activity and degradation properties, comprising: reacting MgCl 2 Dissolving ultrapure water to form a solution a; adding ammonia water and anhydrous ethanol into the solution a under stirring to form solution b, filtering, washing to separate Mg (OH) 2 And (4) precipitating. The precipitate is calcined at high temperature for a period of time to obtain MgO. Subsequently dispersing it in H 2 O 2 To form a suspension c, and separating the solid from the suspension to obtain MgO as a product 2 . Adding MgO 2 Ultrasonically mixing with polyetherimide to obtain suspension d, centrifuging and washing for several times, adding gold nanoparticles into the resuspended d, ultrasonically treating, washing, and resuspending to form gold nanoparticles and MgO 2 The complex of (a); soaking carbon nanotube sponge in the gold nanoparticles and MgO 2 Forming a nanocomposite substrate. The method of the invention is carried out with MgCl 2 Synthesis of MgO for precursors 2 And then the nano composite substrate with SERS activity and degradation performance is respectively assembled with the gold nanoparticles and the carbon nanotube sponge.

Description

Nano composite substrate with SERS activity and degradation performance and preparation method thereof
Technical Field
The invention relates to degradation and SERS activity, in particular to a preparation method of a nano composite substrate with SERS activity and degradation performance.
Background
In a typical Fenton reaction, H 2 O 2 Are commonly used as oxidizing agents to degrade organic contaminants. However, liquid hydrogen peroxide is unstable and has high biotoxicity at high concentrations. Therefore, high-purity magnesium peroxide (MgO) is used 2 ) Nanoparticles and their use in place of H 2 O 2 Degrading the organic dye. Gold nanoparticles as a noble metal, orThe ions are adsorbed on the surface of the noble metal, and can generate a strong Surface Enhanced Raman Scattering (SERS) signal under the irradiation of laser, but the prepared nano material is difficult to recycle. In addition, the dispersed catalyst and reinforcing material are difficult to recover, and cause secondary pollution to the environment. The carbon-based material has larger specific surface area and pore structure, so that the carbon-based material can adsorb organic pollutants in a water body, and simultaneously, the material for carrying out catalytic reaction is loaded and recovered.
Disclosure of Invention
The invention aims to provide a preparation method of a nano composite material with SERS activity and degradation performance, which solves the problem of single function of the material and solves the problem of non-recoverable multifunctional nano material through assembling with carbon nanotube sponge.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for preparing a nanocomposite substrate with SERS activity and degradation properties, comprising the steps of:
s1: mixing MgCl 2 Dissolving in ultrapure water to form a solution a; adding ammonia water and anhydrous ethanol into the solution a under stirring to form solution b, filtering, washing to separate Mg (OH) 2 Precipitating;
s2: calcining the precipitate at a high temperature for a period of time to obtain MgO;
s3: subsequently dispersing it in H 2 O 2 To form a suspension c, and separating the solid from the suspension to obtain MgO as a product 2 ；
S4: adding MgO 2 Ultrasonically mixing with polyetherimide to obtain a suspension d, and centrifuging and washing for several times;
s5: adding gold nanoparticles into the resuspended d, ultrasonically treating for a period of time, centrifugally washing for several times, and forming gold nanoparticles and MgO after resuspension 2 The complex of (a);
s6: soaking carbon nanotube sponge in gold nanoparticles and MgO 2 In the composite of (1), a nanocomposite substrate is formed.
Preferably, in step S3, H 2 O 2 Concentration of (2)The content was 30%.
As a preferable technical solution, the step S4 includes: adding MgO 2 Ultrasonically mixing with polyetherimide to obtain suspension d, and centrifuging and washing for several times; the concentration of the polyetherimide is 0.01%, ultrasonic treatment is carried out at normal temperature for 2h, and the centrifugal washing times with ultrapure water are 6 times.
Preferably, the step S5 includes: adding gold nanoparticles into the resuspended d, performing ultrasonic treatment at normal temperature for 2h, centrifuging and washing with ultrapure water for 4 times, and forming gold nanoparticles and MgO after resuspension 2 The complex of (1).
As a preferable technical solution, the step S6 includes: acidifying carbon nano-sponge, and soaking the carbon nano-sponge in gold nanoparticles and MgO 2 In the composite of (1), a nanocomposite substrate is formed.
The invention also provides the nano composite substrate with SERS activity and degradation performance prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
the method of the present invention is MgO 2 And gold nano particles are self-assembled through static electricity. Using MgO 2 The degradation performance of the gold nanoparticles and the surface plasma resonance effect of the gold nanoparticles are combined to realize the multifunctional property of the material;
the method of the invention utilizes the strong adsorption property of the carbon material to adsorb and enrich the organic pollutants, and then loads the composite material, thereby improving the problem that the dispersed catalyst is difficult to recover.
Drawings
FIG. 1 (a) MgO 2 X-ray powder diffractogram (XRD); (b) MgO (magnesium oxide) 2 X-ray powder diffraction Pattern (XRD) of @ Au;
FIG. 2 (a) MgO 2 Scanning Electron Micrographs (SEM); (b) MgO (magnesium oxide) 2 Scanning Electron Microscopy (SEM) of @ Au; (c) MgO (magnesium oxide) 2 The ultraviolet picture of @ Au degradation of organic pollutants; (d) MgO (magnesium oxide) 2 @ Au assay 10 -4 The SERS spectrogram of the M organic pollutant;
FIG. 3 (a) MgO Supported sponge 2 Scanning Electron Microscopy (SEM) of @ Au; (b) Sponge negativeMgO carrier 2 And SERS spectra before and after the @ Au composite material degrades organic pollutants.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples
1、MgO 2 The synthesis method of @ Au comprises the following steps:
mixing MgCl 2 Dissolving ultrapure water to form a solution a; adding ammonia water and absolute ethyl alcohol into the solution a under the condition of continuous stirring to form solution b, filtering the solution b, washing and separating out Mg (OH) 2 And (4) precipitating. The precipitate is calcined at high temperature for a period of time to obtain MgO. Subsequently dispersing it in H 2 O 2 To form a suspension c, separating the solid from the suspension to obtain the product MgO 2 . Adding MgO 2 Ultrasonically mixing with polyetherimide to obtain suspension d, centrifuging and washing for several times, adding gold nanoparticles into the resuspended d, ultrasonically washing for a period of time, centrifuging and washing for several times, and re-suspending to form gold nanoparticles and MgO 2 The complex of (1). FIG. 1 shows MgO obtained by the above experimental conditions 2 And MgO 2 XRD of @ Au. The XRD pattern (1 a) shows that the obtained product is MgO with better crystallinity 2 FIG. 1b shows MgO 2 The complex with the gold nanoparticles is successfully self-assembled through electrostatic interaction. FIG. 2 (a) shows MgO 2 The Scanning Electron Microscope (SEM) of (b) is MgO 2 Scanning Electron Microscopy (SEM) of @ Au, in which it can be seen from FIGS. 2 (a) and 2 (b) that magnesium peroxide has a bulk structure in which nanoparticles having a small particle size are stacked; mgO with very small particle size is adhered to the surface of gold nano-particles with the particle size of about 70nm 2 . FIG. 2 (c) shows MgO 2 The @ Au ultraviolet graph degrades organic pollutants, and the result shows that the compound can effectively degrade the organic pollutants. FIG. 2 (d) shows MgO 2 @ Au assay 10 -4 The SERS spectrogram of the M organic pollutant can be analyzed to obtain that the compound has SERS activity.
2. MgO loaded carbon nanotube sponge 2 @Au：
Soaking carbon nanotube sponge in the gold nanoparticles and MgO 2 Forming a nanocomposite substrate. FIG. 3 (a) MgO Supported sponge 2 Scanning Electron Microscopy (SEM) of @ Au; (b) Sponge-loaded MgO 2 SERS spectra before and after organic pollutant degradation of @ Au composite material. SEM image shows MgO 2 The @ Au nanocomposite was successfully attached to the sponge. Fig. 3 (b) illustrates that the material is supported on a sponge, which does not affect the performance of the material, and the sponge can perform a good collection function for the dispersed catalyst.

Claims (6)

1. A method for preparing a nanocomposite substrate with SERS activity and degradation properties, comprising the steps of:
s1: mixing MgCl 2 Dissolving in ultrapure water to form a solution a; adding ammonia water and absolute ethyl alcohol into the solution a under the condition of continuous stirring to form solution b, filtering the solution b, washing and separating out Mg (OH) 2 Precipitating;
s2: calcining the precipitate at a high temperature for a period of time to obtain MgO;
s3: subsequently dispersing it in H 2 O 2 To form a suspension c, separating the solid from the suspension to obtain the product MgO 2 ；
S4: adding MgO 2 Ultrasonically mixing with polyetherimide to obtain suspension d, and centrifuging and washing for several times;
s5: adding gold nanoparticles into the resuspended d, ultrasonically treating for a period of time, centrifugally washing for several times, and forming gold nanoparticles and MgO after resuspension 2 The complex of (a);
s6: soaking carbon nanotube sponge in gold nanoparticles and MgO 2 In the composite of (1), a nanocomposite substrate is formed.
2. The method according to claim 1, wherein the reaction mixture is heated to a temperature higher than the melting point of the reaction mixtureIn said step S3, H 2 O 2 The concentration of (2) is 30%.
3. The method according to claim 1, wherein the step S4 includes: adding MgO 2 Ultrasonically mixing with polyetherimide to obtain suspension d, and centrifuging and washing for several times; the concentration of polyetherimide is 0.01%, ultrasonic treatment is carried out at normal temperature for 2h, and the centrifugal washing times with ultrapure water are 6 times.
4. The method according to claim 1, wherein the step S5 includes: adding gold nanoparticles into the resuspended d, performing ultrasonic treatment at normal temperature for 2h, centrifuging and washing with ultrapure water for 4 times, and forming gold nanoparticles and MgO after resuspension 2 The complex of (1).
5. The method according to claim 1, wherein the step S6 includes: acidifying carbon nano-sponge, and soaking the carbon nano-sponge in gold nanoparticles and MgO 2 In the composite of (1), a nanocomposite substrate is formed.
6. A nanocomposite substrate having SERS-activity and degradation properties produced by the method of any one of the preceding claims.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105728742A (en) * 2016-02-18 2016-07-06 陈羽 Preparation method for Au nanometer material/Au-metallic oxide nano-composite material
CN106323940A (en) * 2016-08-24 2017-01-11 合肥学院 Method for in situ monitoring visible photocatalysis and organic dye degradation based on superficially reinforced Raman spectra technology
CN107986241A (en) * 2017-11-29 2018-05-04 华中科技大学 A kind of preparation method of high stable nano magnesium peroxide and products thereof
CN110312680A (en) * 2017-01-11 2019-10-08 通用电气(Ge)贝克休斯有限责任公司 Carbon nano-structured film-substrate and correlation technique including crosslinking
CN110508270A (en) * 2019-09-16 2019-11-29 中南大学 A kind of magnesia/carbon nano tube compound material and the preparation method and application thereof
WO2020087157A1 (en) * 2018-10-29 2020-05-07 Memorial University Of Newfoundland Substrate with magnetic layer for sers, methods for their preparation and uses thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105728742A (en) * 2016-02-18 2016-07-06 陈羽 Preparation method for Au nanometer material/Au-metallic oxide nano-composite material
CN106323940A (en) * 2016-08-24 2017-01-11 合肥学院 Method for in situ monitoring visible photocatalysis and organic dye degradation based on superficially reinforced Raman spectra technology
CN110312680A (en) * 2017-01-11 2019-10-08 通用电气(Ge)贝克休斯有限责任公司 Carbon nano-structured film-substrate and correlation technique including crosslinking
CN107986241A (en) * 2017-11-29 2018-05-04 华中科技大学 A kind of preparation method of high stable nano magnesium peroxide and products thereof
WO2020087157A1 (en) * 2018-10-29 2020-05-07 Memorial University Of Newfoundland Substrate with magnetic layer for sers, methods for their preparation and uses thereof
CN110508270A (en) * 2019-09-16 2019-11-29 中南大学 A kind of magnesia/carbon nano tube compound material and the preparation method and application thereof

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