CN114904537B - Preparation method and application of coaxial cable type bi-component composite material - Google Patents

Preparation method and application of coaxial cable type bi-component composite material Download PDF

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CN114904537B
CN114904537B CN202210551740.9A CN202210551740A CN114904537B CN 114904537 B CN114904537 B CN 114904537B CN 202210551740 A CN202210551740 A CN 202210551740A CN 114904537 B CN114904537 B CN 114904537B
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pda
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CN114904537A (en
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金爽
陈哲
黄强
陈奕倩
张亮
韩丹丹
郑金池
罗源
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State Grid Corp of China SGCC
North China Electric Power University
Electric Power Research Institute of State Grid Xinjiang Electric Power Co Ltd
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North China Electric Power University
Electric Power Research Institute of State Grid Xinjiang Electric Power Co Ltd
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Abstract

The invention discloses a preparation method and application of a coaxial cable type bi-component composite material, which belong to the technical field of inorganic nano materials. The Fe is 2 O 3 ‑Au@SiO 2 Fe in catalyst 2 O 3 The nanowire and the Au NPs exist in a non-contact form and are free of Fe of a cavity 2 O 3 ‑Au@SiO 2 Compared with the catalyst, fe of the invention 2 O 3 ‑Au@SiO 2 The catalyst has better catalytic performance; the bi-component composite material has high catalytic degradability and good circularity for organic pollutants as a photocatalyst. The invention has simple process, strong operability, low production cost and no discharge of three wastes, and is suitable for industrial production.

Description

Preparation method and application of coaxial cable type bi-component composite material
Technical Field
The invention belongs to the technical field of inorganic nano materials. In particular to a preparation method and application of a coaxial cable type bi-component composite material,
background
Fe 2 O 3 The semiconductor is a simple and easily available narrow-band n-type semiconductor (eg=2.1 eV) with low price, can absorb about 40% of solar spectrum energy, and has good chemical stability in aqueous solution with pH value more than 3. However, fe 2 O 3 Low photoconductivity, high recombination rate of electrons and holes, and hole diffusion length, and limited photocatalytic activity. In order to improve the photocatalytic activity, researchers have improved the photocatalytic activity by constructing heterojunctions, composite materials, and the like.
Noble metal Nanoparticles (NPs) have been widely used as catalysts for reactions such as pollutant degradation, water-splitting hydrogen production, carbon dioxide reduction, etc. However, since noble metal nanoparticle catalysts have higher surface energy, they tend to be unstable during catalysis, and severe aggregation tends to occur, resulting in rapid catalyst deactivation; moreover, because the noble metal nano-particle catalyst has small volume and difficult recovery, the noble metal nano-particle catalyst is prevented from being widely applied to heterogeneous catalysis, so that the noble metal nano-particle is fixed on a proper carrier, and the stability and the circularity of the noble metal nano-particle catalyst are improved. Meanwhile, the plasma resonance effect of the noble metal nano particles can effectively improve the photocatalysis performance of the catalyst, the noble metal nano particles can increase the absorption range and the absorption strength of visible light, improve the separation of electron hole pairs, reduce the recombination rate of electrons and holes and enhance the photocatalysis performance.
CN105797750a discloses a Cu 2 O/Au-Fe 2 O 3 Photocatalyst, preparation method and application thereof, and is characterized in that Fe is used as a core 2 O 3 Based on the noble metal Au, the composite semiconductor photocatalyst Cu 2 O, preparation of Cu 2 O/Au-Fe 2 O 3 Photocatalyst of the Cu 2 O/Au-Fe 2 O 3 The loading of Au in the photocatalyst is 0.5-5 wt%, cu 2 The load of O is 2.5-20wt% and is applied to the treatment of phenol-containing wastewater. The degradation effect of the catalyst on phenol in water is general, and the degradation effect on other organic pollutants in water is not mentioned.
In the catalytic field, two-component catalysts are more common and widely used. The multi-component synergistic catalytic effect of the catalyst can obviously improve the catalytic performance, and most of the prior art adopts two catalytic components to mutually contact to improve the overall catalytic performance.
Therefore, there is a need for a two-component or multi-component catalyst that can modulate the electronic energy state of a catalytic system by means of nanoscale or even millimeter nanoscale spaces and interfacial confinement effects, so as to achieve the goal of improving catalytic performance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a coaxial cable type bi-component composite material; the preparation method is characterized by comprising the following steps of:
(1) Respectively dissolving ferric nitrate and potassium hydroxide in deionized water, uniformly mixing, stirring, preparing FeOOH nanowires by adopting a hydrothermal method, and calcining in air to obtain Fe 2 O 3 A nanowire;
(2) The dopamine hydrochloride is subjected to polymerization reaction in a weak alkaline solution to obtain a polydopamine lamellar PDA serving as a sacrificial layer, and the polydopamine lamellar PDA is coated with Fe 2 O 3 Nano-wire, fe is prepared 2 O 3 /PDA；
(3) Reducing chloroauric acid into gold nano-particles Au NPs by stannous chloride reduction method, and loading the gold nano-particles Au NPs on a polydopamine layer to prepare Fe 2 O 3 PDA/Au complex;
(4) Ammonia water and tetraethyl silicate are used as raw materials, and a Stober method is adopted in Fe 2 O 3 Coating SiO on PDA/Au composite 2 Layer, fe is prepared 2 O 3 /PDA/Au/SiO 2 A complex;
(5) Fe is added to 2 O 3 /PDA/Au/SiO 2 Calcining the compound in air to remove the sacrificial layer PDA to obtain the hollow coaxial cable type Fe 2 O 3 -Au@SiO 2 A complex.
The molar ratio of the ferric nitrate to the potassium hydroxide in the step (1) is 1: 3-1: 4, the reaction temperature of the hydrothermal method is 100 ℃ and the reaction time is 12-15 h; calcining at 400-500 deg.c for 3-5 hr to obtain Fe with 20-40 nm diameter 2 O 3 A nanowire.
The weakly alkaline solution in the step (2) is a tris (hydroxymethyl) aminomethane buffer solution, the pH is 8-9, and the reaction time is 12-15 h; the consumption of the dopamine hydrochloride in the step (2) is 20-400 mg, and the thickness of the polydopamine thin layer is 5 ～ 40nm。
The consumption of the dopamine hydrochloride in the step (2) is 20-400 mg, and the thickness of the polydopamine thin layer is 5-40 nm.
The molar ratio of stannous chloride to chloroauric acid in the step (3) is 1:50-100; the diameter of the Au nano-particles Au NPs obtained in the step (3) is 5-15nm, and the average diameter of the Au NPs is 10nm.
The concentration of ammonia water in the step (4) is 0.1-0.15 mol/L, and the concentration of tetraethyl silicate is 4.10 < -6 > -8.10 < -6 > mol/L
Fe in the step (5) 2 O 3 /PDA/Au/SiO 2 The calcination temperature of the compound in the air is 400-500 ℃, and the calcination is carried outThe time is 3-5 h.
The poly-dopamine thin layer PDA serving as the sacrificial layer in the step (2) controls Fe by controlling the thickness of the sacrificial layer 2 O 3 Distance of nanowire and gold nanoparticle Au NPs; the thickness of the produced polydopamine gradually increases with the increase of the amount of dopamine hydrochloride in the range of 5-40nm, thus leading to Fe 2 O 3 The distance between the nanowire and the Au NPs is gradually increased.
The application of the coaxial cable type bi-component composite material is characterized in that the application of the coaxial cable type bi-component composite material in a catalyst, in particular to the prepared Fe 2 O 3 -Au@SiO 2 The application of the compound in a catalyst or a photocatalyst; the Fe is 2 O 3 -Au@SiO 2 The compound can catalyze and degrade chlorophenols and antibiotics; the chlorophenols comprise bisphenol A (BPA), o-chlorophenol (2-CP), p-chlorophenol (4-CP), 2, 4-dichlorophenol (2, 4-2 CP) and 2,4, 6-trichlorophenol (2, 4,6-3 CP), and the antibiotic is Ciprofloxacin (CIP).
The photocatalyst can efficiently remove organic pollutants under the condition of photo Fenton reaction, and has good recycling property, wherein Au NPs and Fe 2 O 3 The photocatalysis performance is best when the nanowire distance is 25 nm.
The Fe is 2 O 3 -Au@SiO 2 Main catalyst Fe of composite 2 O 3 The nano wires and the promoter gold nano particles Au NPs are wrapped on SiO in a non-contact manner 2 In the layer, promoter Au NPs is attached to SiO 2 On the inner wall of the (2), a polydopamine layer PDA is used as a sacrificial layer, and the Fe of the composite material is accurately regulated and controlled by controlling the dosage of raw material dopamine hydrochloride of the polymerization reaction 2 O 3 -Au@SiO 2 The relative positions of the components within the confined environment; the purpose of accurately regulating and controlling the relative positions of the main catalyst and the auxiliary catalyst in the composite catalyst in nanometer scale can be achieved.
The beneficial effects of the invention are as follows: the coaxial cable type bi-component composite material prepared by the preparation method of the invention and the application of the coaxial cable type bi-component composite materialDegrading organic pollutants in photocatalysis. The relative positions of the two components or the multiple components can be accurately regulated and controlled by controlling the thickness of the sacrificial layer, so that the aim of accurately regulating and controlling the relative positions of the main catalyst and the auxiliary catalyst in the composite catalyst in a nanometer scale can be fulfilled. The Fe is 2 O 3 -Au@SiO 2 Fe in catalyst 2 O 3 The nanowire and the Au NPs exist in a non-contact form and are free of Fe of a cavity 2 O 3 -Au@SiO 2 Compared with the catalyst, fe of the invention 2 O 3 -Au@SiO 2 The catalyst has better catalytic performance; the bi-component composite material has high catalytic degradability and good circularity for organic pollutants as a photocatalyst. The invention has general applicability to the preparation of materials in the field of finite field catalysis, and also provides a foundation and a new idea for the development of a novel efficient multi-element catalytic system.
Drawings
FIG. 1 shows Fe in example 1 2 O 3 SEM image of nanowires.
FIG. 2 is Fe in example 1 2 O 3 Transmission electron microscope TEM image of PDA compound.
FIG. 3 (a) is Fe 2 O 3 -Au@SiO 2 TEM overview of the composite; (b) Is Fe 2 O 3 -Au@SiO 2 TEM partial image of the composite;
FIG. 4 is Fe 2 O 3 /Au/SiO 2 X-ray diffraction XRD pattern of the composite.
FIG. 5 is Fe 2 O 3 -Au@SiO 2 A TEM image of the composite, comprising:
a. 2 3 2 2 3 2 .FeO-Au@SiO-5nm；b,FeO-Au@SiO-15nm；c.Fe 2 O 3 -Au@SiO 2 -25nm；
d.Fe 2 O 3 -Au@SiO 2 -40 nm；
FIG. 6 is a graph comparing photocatalytic performance of the photocatalytic materials of example 1 and comparative examples 1-4 for degrading 2-CP.
FIG. 7 is Fe 2 O 3 /Au/SiO 2 Composite catalytic material degradation 2-A comparison graph of photocatalytic performance of CP, comprising: fe (Fe) 2 O 3 -Au@SiO 2 -5 nm、Fe 2 O 3 -Au@SiO 2 -15 nm、Fe 2 O 3 -Au@SiO 2 -25 nm、 Fe 2 O 3 -Au@SiO 2 -40nm and Cavity-free Fe 2 O 3 -au@sio curve;
FIG. 8 is Fe 2 O 3 /Au/SiO 2 Comparison of catalytic cycle performance of the composites.
Detailed Description
The invention provides a preparation method and application of a coaxial cable type bi-component composite material; the preparation method of the coaxial cable type bi-component composite material comprises the following steps:
(1) Respectively dissolving ferric nitrate and potassium hydroxide in deionized water, uniformly mixing, stirring, preparing FeOOH nanowires by adopting a hydrothermal method, and calcining in air to obtain Fe 2 O 3 A nanowire;
(2) The dopamine hydrochloride is subjected to polymerization reaction in a weak alkaline solution to obtain a polydopamine lamellar PDA serving as a sacrificial layer, and the polydopamine lamellar PDA is coated with Fe 2 O 3 Nano-wire, fe is prepared 2 O 3 /PDA；
(3) Reducing chloroauric acid into gold nano-particles Au NPs by stannous chloride reduction method, and loading the gold nano-particles Au NPs on a polydopamine layer to prepare Fe 2 O 3 PDA/Au complex;
(4) Ammonia water and tetraethyl silicate are used as raw materials, and a Stober method is adopted in Fe 2 O 3 Coating SiO on PDA/Au composite 2 Layer, fe is prepared 2 O 3 /PDA/Au/SiO 2 A complex;
(5) Fe is added to 2 O 3 /PDA/Au/SiO 2 Calcining the compound in air to remove the sacrificial layer PDA to obtain the hollow coaxial cable type Fe 2 O 3 -Au@SiO 2 A complex.
The invention will be further described with reference to the drawings and examples,
the medicines used in the examples of the present invention were purchased from Beijing Limited, a national pharmaceutical group chemical reagent. The materials or chemicals used in the examples of the present invention, unless otherwise specified, were obtained by conventional commercial means.
Example 1
Hollow coaxial cable type bi-component catalyst Fe capable of accurately regulating and controlling component positions 2 O 3 -Au@SiO 2 Is prepared by the following steps:
(1) Dissolving 4.85g of ferric nitrate and 2.73g of potassium hydroxide in 10ml of deionized water respectively, mixing the ferric nitrate solution and the potassium hydroxide solution, stirring for 30min, pouring the mixed solution into a 50ml hydrothermal kettle, placing the hydrothermal kettle in a 100 ℃ oven for 12h, naturally cooling the hydrothermal kettle to water temperature after the reaction is finished, performing solid-liquid separation by using a centrifuge, alternately washing with water and ethanol until the supernatant is colorless, placing the reddish brown solid product in a 60 ℃ vacuum drying oven for drying, grinding the product and placing the product in a muffle furnace for calcining for 4h at 500 ℃ to obtain the product Fe 2 O 3 A nanowire.
(2) Weighing the product Fe of (1) 2 O 3 200mg of nanowires are dispersed in 20ml of tris (hydroxymethyl) aminomethane buffer solution (pH is approximately 8.5), uniform suspension is formed by ultrasonic treatment, 200mg of dopamine hydrochloride is added into the suspension, the mixture is stirred for 24 hours at room temperature, and then the mixture is centrifuged, and the supernatant is washed to be colorless by deionized water, and Fe is separated 2 O 3 PDA solid is ready for use.
(3) Fe is added to 2 O 3 PDA was dispersed in 20ml deionized water and sonicated to form a suspension; 0.15g of stannous chloride dihydrate was dissolved in 20ml of hydrochloric acid at a concentration of 0.02 mol/L; stannous chloride solution and Fe 2 O 3 PDA suspension is stirred for 10min, then the product is centrifugally collected, the supernatant is washed to be colorless by deionized water, the solid product is collected and dispersed in 30ml of deionized water, ultrasonic treatment is carried out for 15min, then 250 mu L of 0.0564mol/L chloroauric acid solution is added, the suspension is obtained after stirring for 15min, 0.2g of sodium formate is prepared and dissolved in 10ml of deionized water, the sodium formate solution is poured into the suspension, stirring is continued for 3h, and then the product is centrifugally collected to obtain the compound Fe 2 O 3 /PDA/Au。
(4) Matching withPlacing solution A containing 80ml deionized water, 60ml ethanol and 0.28g CTAB, and mixing the compound Fe 2 O 3 Dispersing PDA/Au in the solution A, ultrasonic treatment for 10min until the suspension is dispersed homogeneously, adding ammonia water 1.14ml into the solution A, adding tetraethyl silicate 200 mu L while stirring, stirring for 6 hr, centrifuging to collect the product, washing the supernatant with deionized water and absolute ethyl alcohol alternately until the supernatant is colorless, stoving the product in vacuum drying oven at 60 deg.c to obtain black powder Fe 2 O 3 /PDA/Au/SiO 2 The composition of the compound and the water,
(5) Calcining the compound obtained in the step (4) in a muffle furnace at 400 ℃ for 4 hours, and removing the sacrificial layer PDA to obtain a product Fe 2 O 3 -Au@SiO 2 Is denoted as Fe 2 O 3 -Au@SiO 2 -25 nm。
Example 2
Only the added amount of dopamine hydrochloride in the step (2) in the example 1 is changed to 20mg, and the other steps are unchanged, so that Fe with the average cavity size of 5nm can be obtained 2 O 3 -Au@SiO 2 Complex, denoted Fe 2 O 3 -Au@SiO 2 -5 nm
Example 3
The Fe with the average cavity size of 15nm can be obtained by only changing the adding amount of the dopamine hydrochloride in the step (2) in the embodiment 1 to 100mg and the other steps to be unchanged 2 O 3 -Au@SiO 2 Complexes, denoted as
Fe 2 O 3 -Au@SiO 2 -15 nm
Example 4
Only the added amount of dopamine hydrochloride in the step (2) in the example 1 is changed to 400mg, and the other steps are unchanged, so that Fe with the average cavity size of 40nm can be obtained 2 O 3 -Au@SiO 2 Complex, denoted Fe 2 O 3 -Au@SiO 2 40-nm comparative example 1
Fe without cavity 2 O 3 -Au@SiO 2 : without the steps (2) and (5) in example 1, the other preparation methods are the same as in example 1, and Fe without cavities can be obtained 2 O 3 -Au@SiO 2 A complex.
Comparative example 2
No carrier is needed, only Fe 2 O 3 I.e. step (1) of example 1.
Comparative example 3
Fe 2 O 3 @SiO 2 : step (1) in example 1 and step (4) in example 1 are the same as those in example 1, and Fe can be obtained 2 O 3 @SiO 2 A complex.
Comparative example 4
Au@SiO 2 : 200mg of Fe obtained in example 1 was weighed out 2 O 3 -Au@SiO 2 Placing the mixture into 20mL of hydrochloric acid solution with the concentration of 2mol/L, stirring for 24 hours, centrifugally collecting a product, washing the product until the supernatant is neutral, placing the product into a vacuum drying oven at the temperature of 60 ℃ and drying to obtain Au@SiOj 2 A complex.
The reddish brown product Fe in example 1 as shown in FIG. 1 2 O 3 Scanning Electron Microscopy (SEM) of nanowires, from which Fe can be seen clearly 2 O 3 Is nanowire-shaped and has an average diameter of about 30nm.
Fe in example 1 as shown in FIG. 2 2 O 3 Transmission Electron Microscopy (TEM) image of PDA complex, it is clear from FIG. 2 that the thin polydopamine layer is uniformly coated on Fe 2 O 3 The surface of the nanowire.
Composite catalyst Fe of example 1 as shown in FIG. 3 2 O 3 -Au@SiO 2 Wherein (a) it can be seen that Au NPs are uniformly dispersed in SiO 2 In the shell, fe 2 O 3 With SiO 2 A significant cavity exists between the two cavities; (b) Fe as a composite catalyst of example 1 2 O 3 -Au@SiO 2 As can be seen from the partial transmission electron microscopy images of (a), the diameter of Au NPs is about 5 to 20nm, and the average particle diameter is about 10nm; the existence and uniform distribution of Fe, au and Si elements can be proved.
FIG. 4 shows Fe obtained in example 1 2 O 3 -Au@SiO 2 The X-ray diffraction pattern (XRD pattern) of the compound has characteristic peaks of 24.1 degrees, 33.2 degrees, 35.6 degrees, 40.9 degrees and 4 degrees9.5 °, 54.1 °, 62.4 °, 64.0 ° and 72.3 °, respectively corresponding α -Fe 2 O 3 (JCPDS No. 33-0664) faces (012), (104), (110), (113), (024), (116), (214), (300) and (119); the strong and sharp peak indicates Fe 2 O 3 The crystallinity is high. In addition, only some weak diffraction peaks were observed at 38.2 °, 44.4 °, 77.5 °, corresponding to the (111), (200), and (311) planes of Au NPs (JCPDS No. 04-0784), indicating that the content of Au NPs is low and the size is small.
FIG. 5 (a-d) shows transmission electron microscope images (TEM images) of the composite catalysts obtained in examples 1-4 with dopamine hydrochloride addition amounts of 20mg, 100mg, 200mg and 400mg, respectively, as clearly seen from the images (a-d), the two-component catalyst Fe with increasing addition amounts 2 O 3 -Au@SiO 2 The size of the cavity is continuously increased, and Fe can be obtained through calculation 2 O 3 And the distances between Au NPs, i.e. the average values of cavity sizes, are 5nm, 15nm, 25nm, 40nm, respectively.
In the preparation method of the embodiment of the invention, when the dopamine hydrochloride is 20mg, the cavity thickness is 1.8nm, 5.1nm and 9.4nm respectively, and the average value of the cavity size is 5nm;
in the preparation method of the embodiment of the invention, when the dopamine hydrochloride is 100mg, the cavity thickness is respectively 12.5nm, 17.8nm and 23.4nm, and the average value of the cavity size is 15nm;
in the preparation method of the embodiment of the invention, when the dopamine hydrochloride is 200mg, the cavity thickness is 21.1nm, 40.1nm, 43.0nm and 47.8nm respectively, and the average value of the cavity size is 25nm;
in the preparation method of the embodiment of the invention, when the dopamine hydrochloride is 400mg, the cavity thickness is 31.2nm, 45.2nm, 68.2nm and 71.1nm respectively, and the average value of the cavity size is 40nm.
The specific operation of the photocatalytic reaction is as follows: adjusting the pH value of the pollutant water solution to 3-5 by using 0.1mol/L hydrochloric acid, and adding a photocatalyst Fe 2 O 3 -Au@SiO 2 Mixing with pollutant water solution, desorbing, balancing, adding H 2 O 2 I.e. degradation begins.
Further, catalytic degradation was performed according to the following method: preparing 20mg/L pollutant solution at room temperature of 25 ℃, adjusting the pH value of the pollutant solution to 3-5 by 0.1mol/L hydrochloric acid, uniformly mixing 20mg of Fe2O3-Au@SiO2 catalyst with the pollutant solution, stirring for 30min in a dark place to reach adsorption-resolution balance, and sampling. 100ml H2O2 was added to start the reaction, samples were taken at regular intervals, and the sample solution was filtered through 0.45 μm aqueous polyethersulfone and the concentration of the contaminants was measured by high performance liquid chromatography.
The composite material catalyst can achieve the aim of recycling, and can be dried after washing before use and then recycled.
Application example 1
Fe prepared in example 1 2 O 3 -Au@SiO 2 -25nm complex as catalyst, 50ml of 20mg/L contaminant solutions of 2-CP, BPA, 4-CP, 2,4-2CP, 2,4,6-3CP, CIP were prepared, respectively, each adjusted to ph=4 with 0.1mol/L HCl; fe with diameter of 25nm 2 O 3 -Au@SiO 2 Adding 20mg of catalyst into each pollutant solution, stirring for 30min in a dark place to reach adsorption-analysis balance, and sampling; then 100ml of H are added respectively 2 O 2 Sampling at fixed intervals at the beginning of timing, filtering the sample liquid by using 0.45 mu m water system polyethersulfone, and measuring the concentration of pollutants by using a high performance liquid chromatograph to obtain the degradation rate and degradation rate of various organic pollutants, wherein the results are shown in Table 1.
Application example 2
50ml of 20 mg/L2-CP pollutant is prepared by taking the comparative material of the example 2 as a catalyst, the pH=4 of the pollutant is regulated by 0.1mol/L HCl, 20mg of different comparative catalysts are dispersed into the pollutant solution, and the mixture is stirred for 30min in a dark place to reach adsorption-analysis balance, and the sample is taken. Then 100ml of H are added 2 O 2 The reaction was started at a fixed time interval, the sample was filtered through a 0.45 μm aqueous polyethersulfone filter, and the concentration of the contaminants was measured by a high performance liquid chromatograph, and the results are shown in FIG. 6.
TABLE 1
Application example 3
Fe with different cavity sizes 2 O 3 -Au@SiO 2 50ml of 20 mg/L2-CP pollutant is prepared for the catalyst, the pH=4 of the pollutant is regulated by 0.1mol/L HCl, 20mg of different comparison catalysts are dispersed into the pollutant solution, and the mixture is stirred for 30min in a dark place to reach adsorption-analysis balance, and is sampled. Then 100ml H2O2 was added, the reaction was started, sampling was performed at regular intervals, the sample solution was filtered through a 0.45 μm aqueous polyethersulfone filter, and the concentration of the contaminants was measured by a high performance liquid chromatograph, and the results are shown in FIG. 7.
Fig. 6 is a graph showing the comparison of photocatalytic performance of different materials of examples and comparative examples, as can be seen from the graph.
The Fe capable of precisely controlling the size of the cavity 2 O 3 -Au@SiO 2 The composite material catalyst has optimal performance, the degradation rate of 30min can reach 99.1 percent, and the Fe has no cavity 2 O 3 -Au@SiO 2 The degradation rate of 60min is about 80 percent, which is inferior to the Fe of the invention 2 O 3 -Au@SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Pure Fe 2 O 3 Nanowire and Cavity-free Fe 2 O 3 -Au@SiO 2 Equivalent; fe (Fe) 2 O 3 -SiO 2 Performance ratio of pure Fe 2 O 3 The degradation rate was about 67.4% in 60min, the outermost SiO was seen 2 Layer pair Fe 2 O 3 The catalysis has a blocking effect; under the condition of photo Fenton reaction, au-SiO 2 The degradation rate in 60min is only 40%.
FIG. 7 shows Fe of examples 1-4 with different cavity sizes 2 O 3 -Au@SiO 2 As can be seen from the comparison of the photocatalytic performance of the composite, as the size of the cavity increases, the degradation rate increases and the Fe without the cavity 2 O 3 -Au@SiO 2 、 Fe 2 O 3 -Au@SiO 2 -5nm、Fe 2 O 3 -Au@SiO 2 -15nm、Fe 2 O 3 -Au@SiO 2 -25nm、Fe 2 O 3 -Au@SiO 2 The degradation rate of 45min corresponding to 40nm is 74.1%, 84.3%, 90.5% and 10 respectively0%, 90.4%. Fe according to the invention 2 O 3 -Au@SiO 2 The-25 nm has the best catalytic performance, because the composite catalyst absorbs light and is refracted and reflected in the cavity many times, so that the utilization rate of the absorbed light is higher. However, as the cavity size increases, catalytic performance begins to decrease, possibly due to photogenerated electrons toward Fe 2 O 3 Too long a surface migration distance results in enhanced charge recombination, leading to reduced catalytic performance.
FIG. 8 shows a composite catalyst Fe according to the invention 2 O 3 -Au@SiO 2 The cyclic utilization diagram of the catalytic degradation 2-CP shows that the degradation rate is 77.6% after the catalyst is recycled for 5 times, indicating that the composite material catalyst Fe of the invention 2 O 3 -Au@SiO 2 Has good recycling performance.
In summary, the composite catalyst Fe of the invention 2 O 3 -Au@SiO 2 The polydopamine layer is used as a sacrificial layer, so that the relative positions of all components in the compound can be accurately regulated and controlled, and further, the aim of accurately regulating and controlling the relative positions of the main catalyst and the auxiliary catalyst in the compound catalyst in a nanometer scale can be achieved. In other words, fe obtained by the present invention 2 O 3 -Au@SiO 2 Fe in catalyst 2 O 3 The nanowire and Au NPs exist in a non-contact form and can be used as a photoFenton reaction catalyst to catalyze and degrade organic pollutants and Fe without a cavity 2 O 3 -Au@SiO 2 Compared with the catalyst, fe of the invention 2 O 3 -Au@SiO 2 Has better catalytic performance and recycling performance.

Claims (1)

1. The preparation method of the coaxial cable type bi-component composite material capable of being used as the photo-Fenton reaction catalyst is characterized by comprising the following steps of:
(1) Respectively dissolving 4.85g of ferric nitrate and 2.73g of potassium hydroxide in 10ml of deionized water, then mixing the ferric nitrate solution and the potassium hydroxide solution, stirring for 30min, pouring the mixed solution into a 50ml hydrothermal kettle, placing the hydrothermal kettle in a 100 ℃ oven for 12h, and after the reaction is completed, standing the hydrothermal kettleCooling to water temperature, performing solid-liquid separation by using a centrifuge, alternately washing with water and ethanol until the supernatant is colorless, drying the reddish brown solid product in a vacuum drying oven at 60 ℃, grinding the dried product, and calcining the ground product in a muffle furnace at 500 ℃ for 4 hours to obtain the product Fe 2 O 3 A nanowire;
(2) Weighing the product Fe of (1) 2 O 3 200mg of nanowire is dispersed in 20ml of tris (hydroxymethyl) aminomethane buffer solution with pH of approximately 8.5, uniform suspension is formed by ultrasonic treatment, 200mg of dopamine hydrochloride is added into the suspension, the mixture is stirred for 24 hours at room temperature, and then the mixture is centrifuged, and the supernatant is washed to be colorless by deionized water, and Fe is separated 2 O 3 PDA solid for standby;
(3) Fe is added to 2 O 3 PDA was dispersed in 20ml deionized water and sonicated to form a suspension; 0.15g of stannous chloride dihydrate was dissolved in 20ml of hydrochloric acid at a concentration of 0.02 mol/L; stannous chloride solution and Fe 2 O 3 PDA suspension is stirred for 10min, then the product is centrifugally collected, the supernatant is washed to be colorless by deionized water, the solid product is collected and dispersed in 30ml of deionized water, ultrasonic treatment is carried out for 15min, then 250 mu L of 0.0564mol/L chloroauric acid solution is added, the suspension is obtained after stirring for 15min, 0.2g of sodium formate is prepared and dissolved in 10ml of deionized water, the sodium formate solution is poured into the suspension, stirring is continued for 3h, and then the product is centrifugally collected to obtain the compound Fe 2 O 3 /PDA/Au；
(4) Solution A containing 80ml deionized water, 60ml ethanol, 0.28g CTAB was prepared and the complex Fe 2 O 3 Dispersing PDA/Au in the solution A, ultrasonic treatment for 10min until the suspension is dispersed homogeneously, adding ammonia water 1.14ml into the solution A, adding tetraethyl silicate 200 mu L while stirring, stirring for 6 hr, centrifuging to collect the product, washing the supernatant with deionized water and absolute ethyl alcohol alternately until the supernatant is colorless, stoving the product in vacuum drying oven at 60 deg.c to obtain black powder Fe 2 O 3 /PDA/Au/SiO 2 The composition of the compound and the water,
(5) Calcining the compound obtained in the step (4) in a muffle furnace at 400 ℃ for 4 hours, and removing the sacrificial layer PDA to obtain a product Fe 2 O 3 -Au@SiO 2 Is denoted as Fe 2 O 3 -Au@SiO 2 -25 nm；
The Fe is 2 O 3 -Au@SiO 2 Main catalyst Fe of composite 2 O 3 The nano wires and the promoter gold nano particles Au NPs are wrapped on SiO in a non-contact manner 2 In the layer, promoter Au NPs is attached to SiO 2 On the inner wall of the (2), a polydopamine layer PDA is used as a sacrificial layer, and the Fe of the composite material is accurately regulated and controlled by controlling the dosage of raw material dopamine hydrochloride of the polymerization reaction 2 O 3 -Au@SiO 2 The relative positions of the components within the confined environment; the aim of accurately regulating and controlling the relative positions of the main catalyst and the auxiliary catalyst in the composite catalyst in the nanometer scale can be achieved; and by exploring the degradation experiment of p-chlorophenol (2-CP), it is found that when Fe 2 O 3 The distance between the nanowire and the Au nanoparticle Au NPs is 25nm, and the catalytic performance is optimal.
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