CN106984335B - A kind of CdS/GE/Fe2O3The preparation method of composite photo-catalyst - Google Patents

A kind of CdS/GE/Fe2O3The preparation method of composite photo-catalyst Download PDF

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CN106984335B
CN106984335B CN201710163541.XA CN201710163541A CN106984335B CN 106984335 B CN106984335 B CN 106984335B CN 201710163541 A CN201710163541 A CN 201710163541A CN 106984335 B CN106984335 B CN 106984335B
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CN106984335A (en
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沈小平
吴佳佳
季振源
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Jiangsu University
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04Sulfides
    • B01J27/043Sulfides with iron group metals or platinum group metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties

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Abstract

The invention belongs to nanocomposite preparation field, in particular to graphene (GE)/γ-Fe of a kind of CdS Nanoparticle Modified2O3The preparation method of composite photo-catalyst.It has main steps that and first synthesizes cube block-like Prussian blue (PB) nano particle with hydro-thermal method;Again in deionized water by PB particle ultrasonic disperse, polyallylamine hydrochloride is added, keeps PB particle positively charged.Uniform graphite oxide dispersion and nitric acid cadmium solution are sequentially added, is stirred.It is eventually adding sodium sulfide solution, is stirred to react, product is collected.By above-mentioned product in argon atmosphere, with 2 DEG C of min‑1Rate be warming up to 350 DEG C, and keep 2h, obtain final product.The composite material is a kind of good visible light catalyst, has photocatalytic degradation effect to organic pollutant Rhodamine B.

Description

A kind of CdS/GE/Fe2O3The preparation method of composite photo-catalyst
Technical field
The invention belongs to nanocomposite preparation field, in particular to a kind of graphene of CdS Nanoparticle Modified (GE)/γ-Fe2O3The preparation method of composite photo-catalyst.
Technical background
Conductor photocatalysis is in recent years in the popular research direction that materials chemistry and Environmental Chemistry crossing domain rise.Light Catalysis technique can be and without secondary pollution at normal temperatures and pressures by most organic pollutant degradations, it has also become has a bright future Environmental pollution improvement's method.The core of photocatalysis technology is catalysis material, traditional catalysis material be metal oxide or Person's sulfide semiconductor compound, this kind of material are limited by self property, and photocatalysis performance is generally lower.For example, TiO2It is to answer With most commonly used photochemical catalyst, but since its band-gap energy is greater than 3.0eV, only just there is catalytic activity under ultraviolet light, Strongly limit its application range.In recent years, two or more semiconductor is intercoupled, forms semiconductor heterostructure Receive the extensive concern of researcher.All solid state Z- type energy band is wherein constructed according to the difference of semiconductor conduction band, valence band location Structural composite material has become a kind of development trend.All solid state Z- type band structure is passed through using the electronics on semiconductor A conduction band It crosses Problem of Electronic Broker and the hole of semiconductor B valence band is combined, leave the electronics on the hole and semiconductor B on semiconductor A, lose The electrons and holes stayed have stronger reduction and oxidability, and furthermore this kind of structure can promote photo-generate electron-hole To efficiently separating, so that semiconductor catalytic performance obtains raising largely.
Graphene (GE) is two-dimentional carbonaceous new material with the fastest developing speed in recent years, except possessing bigger serface, Gao Hua Outside the plurality of advantages for learning traditional Carbon Materials such as stability, preferable adsorption capacity, also because its unique structure makes it have perfectly The special properties such as quantum hall effect, unique quantum tunneling effect, ambipolar electric field effect.The present invention selects band gap phase γ-the Fe matched2O3With CdS respectively as semiconductor A and B, γ-Fe is constructed using graphene as Problem of Electronic Broker2O3/ GE/CdS is multiple Light combination catalyst has prepared the Z- type structure composite catalysis material haveing excellent performance, can be used for Visible Light Induced Photocatalytic organic contamination Object.
Summary of the invention
The purpose of the present invention is to provide a kind of CdS Nanoparticle Modified GE/ γ-Fe2O3The preparation side of composite photo-catalyst Method adopts the following technical scheme that
(1) by PVP and K3Fe(CN)6It is dissolved in HCl solution, mixture is transferred in reaction kettle after mixing evenly, react Natural cooling afterwards obtains Prussian blue (PB) nano cubic block after cleaning.
Described PVP, the K3Fe(CN)6It is respectively as follows: 1.52g:0.044g:20mL with the quality and volume of HCl solution;It is described The concentration of HCl solution is 0.1M.
The temperature of the reaction is 180 DEG C, reaction time 10h.
(2) PB is soluble in water, after ultrasonic disperse, polyallylamine hydrochloride (PAH) solution is added, stirs evenly for the first time After sequentially add graphite oxide dispersion, Cd (NO3)2Solution stirs evenly for the second time;It is eventually adding Na2S solution, third time It stirs evenly, after product is cleaned with deionized water, obtains product PB/GO/CdS.
The PB, water, polyallylamine hydrochloride solution, graphite oxide dispersion, Cd (NO3)2Solution, Na2The ratio of S solution Example is: 5-20mg:40mL:2-4mL:0.5-2.5mL:4-6mL:4-6mL.
Cd (the NO3)2With Na2The ratio between amount of substance of S is 1:1.
The concentration of the polyallylamine hydrochloride solution is 1g/L-1;The concentration of the graphite oxide dispersion is 5mg mL-1;Cd (the NO3)2The concentration of solution is 0.11M;The Na2The concentration of S solution is 0.11M.
First, second and third mixing time is 3h;The time of the ultrasonic disperse is 30min.
(3) product PB/GO/CdS is placed in Ar2In atmosphere, 350 DEG C are warming up to, and keep 2h, obtain final product γ- Fe2O3/GE/CdS。
The heating rate is 2 DEG C of min-1
CdS nanoparticle is closely attached to the surface of graphene in product of the present invention, and CdS partial size is 30- 100nm;γ-Fe simultaneously2O3Nanoparticle is also supported on graphene film, and its pattern is cube bulk, partial size 200nm.This Prepared γ-the Fe of invention2O3/ GE/CdS composite photo-catalyst has not been reported so far, and the present invention is carried on graphite using PB preparation γ-the Fe of alkene on piece2O3Nano cubic block is a brand-new approach.The semiconductor γ-that the present invention selects band gap to match Fe2O3It is photocatalytic activity constituent element with CdS, Z- type structure composite photocatalysis has successfully been constructed using graphene as Problem of Electronic Broker Material-γ-Fe2O3/ GE/CdS makes photogenerated charge be efficiently separated and be utilized.γ-the Fe2O3/ GE/CdS composite photocatalyst Agent not only has excellent visible light catalysis activity, the degradation suitable for organic pollutant;And due to γ-Fe therein2O3Tool There is ferromagnetism, catalyst can easily carry out Magneto separate recycling.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of composite material prepared by the embodiment of the present invention 1.
Fig. 2 is transmission electron microscope (TEM) photo of composite material prepared by the embodiment of the present invention 1.
Fig. 3 is the performance map of the rhodamine B degradation (RhB) of composite material prepared by the embodiment of the present invention 1.Wherein catalyst Dosage be 30mg, RhB dosage be 60mL, concentration be 5mg L-1.Light source is the Xe lamp of 250W, and is removed ultraviolet light with optical filter It removes.
Specific embodiment:
The embodiment of the present invention is described in detail with reference to the accompanying drawing, but protection scope of the present invention is not limited to these Embodiment.
Embodiment 1:
By 10mg PB ultrasonic disperse in 40mL deionized water, 2mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 1mL 5mg mL-1GO solution;5mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 5mL 0.11M2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.
Fig. 1 is the XRD diagram of product, and all diffraction maximums for scheming PB match with JCPDS No.73-0687, corresponding to cube The Fe of phase4[Fe(CN)6]3.For γ-Fe2O3The XRD diagram of/RGO is located at 30.24,35.63,43.28,53.73,57.27, 62.925 and 62.499 ° of diffraction maximum corresponds to (022), (311), (400), (422), (511), and (440) crystal face, with γ- Fe2O3Standard card (JCPDS No 39-1346) match.In γ-Fe2O3In the XRD diagram of/RGO/CdS, in addition to γ- Fe2O3Diffraction maximum, remaining peak can belong to cubic phase CdS (JCPDS No.10-0454).Illustrate that compound is successfully prepared Come.
Fig. 2 is that the TEM of product schemes, wherein figure a is γ-Fe2O3The TEM of/RGO schemes, as can be seen from the figure cubic block γ- Fe2O3It is loaded on redox graphene on piece, figure b is γ-Fe2O3The TEM of/RGO/CdS schemes, it can be seen that not only standing Square γ-Fe2O3It is loaded on redox graphene on piece, and there is also CdS nanoparticles on reduced graphene surface.
Fig. 3 is that the photocatalytic degradation RhB of product schemes.As can be seen from the figure sample can be with degradable pollutant after 1h RhB。
Embodiment 2:
By 5mg PB ultrasonic disperse in 40mL deionized water, 2mL PAH (1g L is added-1) solution, stir 3h;Again successively 1mL 5mg mL is added-1GO solution;5mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 5mL2S is molten Liquid stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is kept 2h obtains final product.
Embodiment 3:
By 15mg PB ultrasonic disperse in 40mL deionized water, 2mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 1mL 5mg mL-1GO solution;5mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 5mL2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.
Embodiment 4:
By 20mg PB ultrasonic disperse in 40mL deionized water, 2mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 1mL 5mg mL-1GO solution;5mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 5mL2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.
Embodiment 5:
By 10mg PB ultrasonic disperse in 40mL deionized water, 3mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 1mL 5mg mL-1GO solution;5mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 5mL2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.
Embodiment 6:
By 10mg PB ultrasonic disperse in 40mL deionized water, 4mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 1mL 5mg mL-1GO solution;5mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 5mL2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.
Embodiment 7:
By 10mg PB ultrasonic disperse in 40mL deionized water, 2mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 2mL 5mg mL-1GO solution;5mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 5mL2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.
Embodiment 8:
By 10mg PB ultrasonic disperse in 40mL deionized water, 2mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 1mL 5mg mL-1GO solution;4mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 4mL2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.
Embodiment 9:
By 10mg PB ultrasonic disperse in 40mL deionized water, 2mL PAH (1g L is added-1) solution, stir 3h;Again according to Secondary addition 1mL 5mg mL-1GO solution;6mL 0.11M CdCl2Solution stirs 3h;It is eventually adding the Na of 0.11 M of 6mL2S Solution stirs 3h.After being cleaned with deionized water, gained sample is placed in argon atmosphere, in 2 DEG C of min-1350 DEG C are warming up to, and is protected 2h is held, final product is obtained.

Claims (10)

1. a kind of CdS/GE/Fe2O3The preparation method of composite photo-catalyst, it is characterised in that specific step is as follows: will be Prussian blue PB is soluble in water, after ultrasonic disperse, polyallylamine hydrochloride solution PAH is added, sequentially adds oxygen after mixing evenly for the first time Graphite alkene dispersion liquid, Cd (NO3)2Solution stirs evenly for the second time;It is eventually adding Na2S solution, stirs evenly for the third time, will After product is cleaned with deionized water, product PB/GO/CdS is obtained;Product PB/GO/CdS is placed in Ar2In atmosphere, it is warming up to 350 DEG C, and 2h is kept, obtain final product CdS/GE/Fe2O3Composite photo-catalyst.
2. a kind of CdS/GE/Fe as described in claim 12O3The preparation method of composite photo-catalyst, it is characterised in that: described Prussian blue PB, water, polyallylamine hydrochloride solution, graphene oxide dispersion, Cd (NO3)2Solution, Na2The ratio of S solution It is: 5-20mg:40mL:2-4mL:0.5-2.5mL:4-6mL:4-6mL;Cd (the NO3)2With Na2The ratio between amount of substance of S is 1:1。
3. a kind of CdS/GE/Fe as described in claim 12O3The preparation method of composite photo-catalyst, it is characterised in that: described The concentration of polyallylamine hydrochloride solution is 1g/L;The concentration of the graphene oxide dispersion is 5mg mL-1;The Cd (NO3)2The concentration of solution is 0.11M;The Na2The concentration of S solution is 0.11M.
4. a kind of CdS/GE/Fe as described in claim 12O3The preparation method of composite photo-catalyst, it is characterised in that: described First, second and third mixing time is 3h;The time of the ultrasonic disperse is 30min.
5. a kind of CdS/GE/Fe as described in claim 12O3The preparation method of composite photo-catalyst, it is characterised in that: described Heating rate is 2 DEG C of min-1
6. a kind of CdS/GE/Fe as described in claim 12O3The preparation method of composite photo-catalyst, it is characterised in that: described The pattern of Prussian blue PB is nano cubic block, using Prussian blue PB nano cubic block as generation γ-Fe2O3Nano cubic The presoma of block;Prussian blue PB is set to become positively charged lotus with polyallylamine hydrochloride, in favor of itself and negatively charged oxidation stone Black alkene is compound;Cd (NO is first added when preparing CdS3)2, afterwards plus Na2S makes positively charged Cd2+It is first adsorbed in surface of graphene oxide, To realize the effective compound of CdS and graphene;In Ar2Heating makes Prussian blue PB be converted into γ-Fe in atmosphere2O3, simultaneously will Graphene oxide thermal reduction is graphene.
7. a kind of CdS/GE/Fe as described in claim 12O3The preparation method of composite photo-catalyst, it is characterised in that: final Fe in product2O3It is closely supported on graphene film with CdS, and Fe2O3For γ-Fe2O3, pattern is cube bulk, partial size is 200nm, CdS partial size are 30-100nm.
8. a kind of CdS/GE/Fe as described in claim 12O3The preparation method of composite photo-catalyst, which is characterized in that described The preparation step of Prussian blue PB is as follows: by PVP and K3Fe(CN)6It is dissolved in HCl solution, after mixing evenly shifts mixture Into reaction kettle, natural cooling after reaction obtains Prussian blue PB nano cubic block after cleaning.
9. a kind of CdS/GE/Fe as claimed in claim 82O3The preparation method of composite photo-catalyst, which is characterized in that described PVP, K3Fe(CN)6It is respectively as follows: 1.52g:0.044g:20mL with the quality and volume of HCl solution;The concentration of the HCl solution For 0.1M.
10. a kind of CdS/GE/Fe as claimed in claim 82O3The preparation method of composite photo-catalyst, which is characterized in that described The temperature of reaction is 180 DEG C, reaction time 10h.
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