CN104549361B - A kind of magnetic noble metal catalyst for strengthening activity with Raman and preparation method thereof - Google Patents
A kind of magnetic noble metal catalyst for strengthening activity with Raman and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of magnetic noble metal catalyst for strengthening activity with Raman and preparation method thereof.The catalyst is formed by noble metal, graphene and magnetic Nano material tri compound.Its preparation method is characterized as depositing Fe in the surface in situ of graphene oxide successively3O4、MnFe2O4、ZnFe2O4、CoFe2O4Deng the noble metal nano particles such as iron-base magnetic nano material and growth Au, Ag, Pt, Pd.Both magnetic responsiveness and externally-applied magnetic field with magnetic-particle are handling for product of the present invention, the characteristics such as efficient absorption, the conduction of graphene nano material, there is the unique optical property of noble metal granule and catalytic performance again, and the cooperative effect between noble metal nano particles and grapheme material can be strengthened surface reinforced Raman active that noble metal original has and catalytic activity, be it is a kind of can be while being used for the magnetic precious metal catalytic material system of the Raman detection of low concentration phenyl ring class organic micro-pollutantses in water, catalysis deoxidization, degradation and enriching and recovering.
Description
Technical field
The invention belongs to nanometer technology, it is related to a kind of magnetic noble metal catalyst with Raman enhancing activity and its preparation
Method.
Background technology
INDUSTRIAL ORGANIC POLLUTANTS, particular with aromatic rings organic pollution largely can long-term existence in environment and biology
In body, detrimental effect is caused to sustainable development of ecological environment, people's health, social safety and economic society etc.,
Thus the environmental problem triggered increasingly attracts attention.Wherein, p-nitrophenol（4-NP）Be a class high toxicity, difficult degradation,
Most it is difficult to the class compound administered, it is the priority pollutants of EPA, is also priority acccess control dirt in China's water
Contaminate the toxic pollutant on thing blacklist.And 4-NP reduzate para-aminophenol（4-AP）Toxicity it is relatively much lower, together
When be important chemical industry and medicine intermediate.Therefore, from solution a small amount of 4-NP detection, enrichment, then to 4-AP conversion, inspection
Survey and reclaim, have important practical significance.
SERS (Surface-enhanced Raman Scattering, SERS) technology can provide it
The information for the molecular level that his detection technique is difficult to obtain, with detection time is short, water interference is small, detection when do not destroy sample
Product, it is not necessary to which complex process is carried out to sample, can direct in-situ analysis, the advantages of detection range is wide, in bioanalysis and environment
Many fields such as pollution detection cause the broad interest of scholars.It is well known that for utilizing NaBH4Reduction 4-NP obtains 4-
AP reaction can only could occur under the catalysis of the noble metals such as Au, Ag, Pd, and noble metal nano particles are conventional Ramans
Strengthen base material, have again recently after document report, noble metal and graphene nano Material cladding, cooperative effect between the two
Can be strengthened surface reinforced Raman active that nano-particle original has and catalytic activity.Therefore, for mentioned above
Demand, we have proposed by magnetic nano-particle with reduction graphene oxide（rGO）Compound be used as micropollution in water
The carrier material of thing processing, by being further combined the noble metal nano particles such as assembling Au, Ag on its surface, design synthesis is same
When magnetic precious metal catalytic material body for the Raman detection of low concentration phenyl ring class organic micro-pollutantses in water and enriching and recovering
System.
The content of the invention
Strengthen magnetic noble metal catalyst and its preparation side of activity with Raman it is an object of the invention to provide a kind of
Method.This method prepare have Raman strengthen activity magnetic noble metal catalyst by noble metal, reduction graphene oxide and
Magnetic Nano material is constituted.Its preparation method is characterized as depositing Fe in the surface in situ of the graphene oxide of reduction successively3O4、
MnFe2O4、ZnFe2O4、CoFe2O4Deng the noble metal nano particles such as iron-base magnetic nano material and growth Au, Ag, Pt, Pd.Should
Composite prepared by the method good dispersion in water, can place the several months without reunion；The matter of noble metal and magnetic nanoparticle
Amount ratio and their particle diameter can be changed by adjusting the concentration of reactant, wherein magnetic and noble metal nano particles
Particle diameter can regulate and control between 100-400 and 20-80 nm respectively.
The concrete technical scheme of the present invention is as follows：
The present invention's there is Raman to strengthen the magnetic noble metal catalyst of activity, and the composite is by the graphite oxide that reduces
Alkene, noble metal and magnetic Nano material tri compound are formed, and its structure is that magnetic nanoparticle and noble metal are loaded simultaneously
In the surface of graphene oxide, the particle diameter of magnetic nanoparticle and noble metal nano particles is respectively 100-400 nm and 20-80
nm；Described magnetic Nano material is Fe3O4、MnFe2O4、ZnFe2O4、CoFe2O4In any one, described noble metal is
Any one in Au, Ag, Pt, Pd.
The present invention's there is Raman to strengthen the preparation method of active magnetic noble metal catalyst, by graphene oxide ultrasound
It is dispersed in ethylene glycol, adds magnetic material precursor, after being stirred at room temperature, sodium acetate and polyethylene glycol are sequentially added, after stirring
Reactor is transferred to, 12-16h is reacted under the conditions of 160-200 DEG C and obtains magnetic-graphene composite material；Reaction is cooled down after terminating
To room temperature, Magneto separate, drying after cleaning are centrifuged repeatedly with ethanol；Above-mentioned magnetic-graphene composite material is taken, secondary water is dispersed in
In, noble metal precursor solution is added, room temperature is cooled to after being warming up to 90-110 DEG C of reaction 10-20min, Magneto separate is produced
Product.
The present invention's there is Raman to strengthen the preparation method of active magnetic noble metal catalyst, comprise the following steps that：
（1）Graphene oxide is prepared using Hummers oxidizing process；
（2）By graphene oxide ultrasonic disperse in 25mL ethylene glycol, in 1mg/mL-5 mg/mL, then its concentration control
0.9-1.8mmol magnetic material precursors are added, are stirred at room temperature after 1-3h, 1.8g sodium acetates is sequentially added and 0.5g is poly-
Ethylene glycol, continues to be transferred to reactor after stirring 0.2-0.8h, 12-16h is reacted under the conditions of 160-200 DEG C and obtains magnetic-graphite
Alkene composite；Reaction is cooled to room temperature after terminating, and Magneto separate after cleaning is centrifuged repeatedly with ethanol, washes 3-5 times, is placed in true
55-65 DEG C of dry 22-26h in empty drying box；
（3）By step（2）The aqueous dispersions that concentration is 0.5-2mg/mL are made in products obtained therefrom configuration, add mass fraction and are
1%-5% noble metal precursor solution 10-200ul, room temperature, magnetic point are cooled to after being warming up to 95-105 DEG C of reaction 13-17min
From product is obtained, wash 3-5 times.
Described magnetic material precursor is FeCl3•6H2O, or FeCl3•6H2O and MCl2•nH2O mixture, M be Co,
Any one in Ni, Zn, Mn, M2+/Fe3+= 0.5；Described noble metal precursor is water-soluble precious metal salt, such as expensive
Manganate of the nitrate of metal, the perchlorate of noble metal and noble metal etc..
The present invention's there is Raman to strengthen the purposes of active magnetic noble metal catalyst：The catalyst is used to be catalyzed to nitre
The reaction of base phenol and sodium borohydride, while adsorption and enrichment can be carried out to reactant and reaction product, and can also pass through
In-situ Raman spectral detection is identified reaction product and catalytic reaction process is tracked.
Compared with the magnetic noble metal catalyst of document report, the magnetic proposed by the present invention with Raman enhancing activity is expensive
Metallic catalyst has the characteristics that：（1）Product gathers multi -function in integral whole, both the magnetic responsiveness with magnetic-particle and additional
Magnetic field is handling, the characteristic such as efficient absorption, conduction of graphene nano material, has the unique optical property of noble metal granule again
And catalytic performance, step enrichment, highly sensitive detection and the Magneto separate of trace contaminant in water can be achieved；（2）Noble metal and graphite
After alkene nano material is compound, cooperative effect between the two can make the surface reinforced Raman active and catalysis that nano-particle original has
Activity is strengthened, and is expected to develop the new device of sensitiveer and effective detection water micropollutants；（3）Prepared is compound
Nano material modified by force, can gather multi -function in integral whole again, be conducive to it in the wide of the fields such as biomedical, catalysis, separation
General application.
Brief description of the drawings
Fig. 1 is respectively prepared (a) Fe3O4- rGO-Au and (b) Fe3O4- rGO-Ag TEM figures.
Fig. 2 is prepared (a) Fe3O4- rGO-Au and (b) Fe3O4- rGO-Ag XRD collection of illustrative plates.
Fig. 3 is respectively with (a) Fe3O4- rGO-Au and (b) Fe3O4- rGO-Ag composites are used as catalyst, NaBH4Also
Former 4-NP time correlation uv-spectrogram.
Fig. 4 is respectively with (a) Fe3O4- rGO-Au and (b) Fe3O4- rGO-Ag composites are used as catalyst, NaBH4Also
Former 4-NP In (C0/Ct) linear relationship chart.
Fig. 5 is with Fe3O4- rGO-Au is catalyst and Raman enhancing base material, in-site detecting NaBH4Reduce 4-NP's
Course of reaction Raman spectrogram.
Fig. 6 is Fe3O4- rGO-Au (a1) and Fe3O4- rGO-Ag (a2) catalyst is mixed with 4-NP solution respectively, and magnetic force is stirred
Mix 30min to reach after adsorption equilibrium, 4-NP uv absorption spectra in solution；With Fe3O4- rGO-Au (b1) and Fe3O4-
RGO-Ag (b2) is catalyst, NaBH4Reduce after 4-NP, Magneto separate, 4-AP uv absorption spectra in solution.
Fig. 7 is with Fe3O4- rGO-Au is catalyst, recycles the influence that number of times reduces 4-NP to catalysis.
Embodiment
Embodiment 1：
GO is first prepared using Hummers oxidizing process.50mg GO are weighed, ultrasonic disperse is added in 25ml ethylene glycol
0.25g FeCl3•6H2O, is stirred at room temperature after 2h, sequentially adds 1.8g NaAc and 0.5g PEG, turns after continuing stirring 0.5h
Enter reactor, 16h is reacted under the conditions of 200 DEG C.Reaction is cooled to room temperature after terminating, and magnetic point after cleaning is centrifuged repeatedly with ethanol
From washing 3 ~ 5 times is placed in 60 DEG C of dry 24h in vacuum drying chamber.
Above-mentioned magnetic-graphene composite material 10mg is taken, by 1mg/mL ultrasonic disperses in 10ml water, mass fraction is added
For 1% chlorauric acid solution 100ul, the 15min that flows back is warming up to after 100 DEG C, room temperature is cooled to, Magneto separate obtains Fe3O4-rGO-
Au composites, are washed 3 ~ 5 times, ultrasonic disperse is in water.
Embodiment 2：
GO is first prepared using Hummers oxidizing process.50mg GO are weighed, ultrasonic disperse is added in 25ml ethylene glycol
0.6mmol FeCl3•6H2O and 0.3mmol MnCl2•4H2O, is stirred at room temperature after 2h, sequentially adds 1.8g NaAc and 0.5g
PEG, continues to be transferred to reactor after stirring 0.5h, 16h is reacted under the conditions of 200 DEG C.Reaction is cooled to room temperature after terminating, and uses second
Alcohol is centrifuged repeatedly Magneto separate after cleaning, washes 3 ~ 5 times, is placed in 60 DEG C of dry 24h in vacuum drying chamber.
Above-mentioned magnetic-graphene composite material 10mg is taken, by 1mg/mL ultrasonic disperses in 10ml water, mass fraction is added
For 1% chlorauric acid solution 200ul, the 15min that flows back is warming up to after 100 DEG C, room temperature is cooled to, Magneto separate obtains MnFe2O4-
RGO-Au composites, are washed 3 ~ 5 times, ultrasonic disperse is in water.
Embodiment 3：
GO is first prepared using Hummers oxidizing process.50mg GO are weighed, ultrasonic disperse is added in 25ml ethylene glycol
0.9mmol FeCl3•6H2O, is stirred at room temperature after 2h, sequentially adds 1.8g NaAc and 0.5g PEG, continues to stir after 0.5h
Reactor is transferred to, 16h is reacted under the conditions of 200 DEG C.Reaction is cooled to room temperature after terminating, and magnetic after cleaning is centrifuged repeatedly with ethanol
Separation, washes 3 ~ 5 times, is placed in 60 DEG C of dry 24h in vacuum drying chamber.
Above-mentioned magnetic-graphene composite material 10mg is taken, by 1mg/mL ultrasonic disperses in 10ml water, mass fraction is added
For 1% silver nitrate solution 50ul, the 15min that flows back is warming up to after 100 DEG C, room temperature is cooled to, Magneto separate obtains Fe3O4-rGO-
Ag composites, are washed 3 ~ 5 times, ultrasonic disperse is in water.
Embodiment 4：
GO is first prepared using Hummers oxidizing process.50mg GO are weighed, ultrasonic disperse is added in 25ml ethylene glycol
0.6mmol FeCl3•6H2O and 0.3mmol MnCl2•4H2O, is stirred at room temperature after 2h, sequentially adds 1.8g NaAc and 0.5g
PEG, continues to be transferred to reactor after stirring 0.5h, 16h is reacted under the conditions of 200 DEG C.Reaction is cooled to room temperature after terminating, and uses second
Alcohol is centrifuged repeatedly Magneto separate after cleaning, washes 3 ~ 5 times, is placed in 60 DEG C of dry 24h in vacuum drying chamber.
Above-mentioned magnetic-graphene composite material 10mg is taken, by 1mg/mL ultrasonic disperses in 10ml water, mass fraction is added
For 1% silver nitrate solution 100ul, the 15min that flows back is warming up to after 100 DEG C, room temperature is cooled to, Magneto separate obtains MnFe2O4-
RGO-Ag composites, are washed 3 ~ 5 times, ultrasonic disperse is in water.
The present invention is in previously prepared graphene nano material surface successively in-situ deposition Fe3O4、MnFe2O4、
ZnFe2O4、CoFe2O4Deng the noble metal nano particles such as iron-base magnetic nano material and growth Au, Ag, Pt, Pd, obtain by expensive
Metal, the graphene oxide of reduction and a kind of of magnetic Nano material composition strengthen the magnetic precious metal catalyst of activity with Raman
Agent.The magnetic and the big I of noble metal nano particles that graphenic surface is supported are by changing iron-based reactant and precious metal ion
Amount adjust.
Using prepared by above method there is Raman to strengthen the magnetic noble metal catalyst good dispersion of activity, number can be placed
The moon, larger lamellar structure was presented in graphene without reuniting, and surface has been covered with magnetic and noble metal nano particles, and particle diameter can divide
Do not regulate and control between 50-400 and 20-80 nm.The big specific surface area of graphene, it is possible to achieve phenyl ring type organic in water
Enrichment；The catalytic activity of chemiluminescence and noble metal nano particles between graphene and noble metal nano particles and
It acts on the SERS signal produced with organic pollution, with reference to the enrichment and the controllability of externally-applied magnetic field of magnetic-particle,
It can simultaneously circulate and realize the Raman detection of low concentration phenyl ring class organic micro-pollutantses in water, catalysis deoxidization, degradation and enriching and recovering.
From Fe3O4- rGO-Au and Fe3O4TEM the and SEM photos of-rGO-Ag samples can be seen that graphene present compared with
Big lamellar structure, surface has been covered with the Fe that particle diameter is about 300nm3O4 And 50nm gold or 45 nm Argent grain, and point
Cloth is uniform, without obvious agglomeration.
From Fe3O4- rGO-Au and Fe3O4The XRD collection of illustrative plates of-rGO-Ag samples can be seen that graphenic surface and load instead
The magnetic Fe of spinel structure3O4Nano-particle and noble metal Au, Ag particles.
From Fe3O4- rGO-Au and Fe3O4- rGO-Ag samples catalysis p-nitrophenol related uv-spectrogram can draw,
When with Fe3O4When-rGO-Au composites are as catalyst, the reaction of sodium borohydride reduction p-nitrophenol is first order kinetics
Reaction, speed constant is 0.500min-1, when with Fe3O4When-rGO-Ag composites are as catalyst, sodium borohydride reduction pair
The reaction of nitrophenol is also reacted for first order kinetics, and speed constant is 0.239min-1, it is shown that superior catalytic performance.
Fig. 5 is with Fe3O4- rGO-Au is catalyst and Raman enhancing base material, and in-site detecting sodium borohydride reduction is to nitre
The course of reaction Raman spectrogram of base phenol, the min of spectral line interval 2.Under initial state, detect positioned at 1345,1113,865
cm-1 To come from the characteristic peak of p-nitrophenol.With the progress of reaction, nitro is located at 1345 cm-1 With 1113 cm-1 's
Vibration performance peak fades away, and illustrates that p-nitrophenol is progressively reduced, and the blob detection of para-aminophenol is less than illustrating to amino
Phenol is not adsorbed by golden nanometer particle.During reduction is catalyzed, nitro is located at 865 cm-1 Characteristic peak gradually increase
By force, and occur in that and progressively enhanced be located at 852 cm-1 With 1287 cm-1 The nitroso characteristic peak of intermediate product, further card
Understand that nitro is first changed into nitroso in catalytic process, with document（Chemical journal, 2011,69: 2368-2372）Report phase
It coincide
, can be with according to Fig. 6 and concentration-absorbance standard curve of reactant p-nitrophenol and product para-aminophenol
Obtain Fe3O4- rGO-Au and Fe3O4- rGO-Ag catalyst respectively may be about 170 to the adsorbance of reactant p-nitrophenol
Mg/g and 148 mg/g, the adsorbance to product para-aminophenol respectively may be about 447 mg/g and 440 mg/g, illustrate us
Prepared catalyst can adsorb a certain amount of reactant and product by π-πconjugation, not result in secondary pollution.
Fig. 7 is with Fe3O4- rGO-Au is catalyst, recycles the influence that number of times reduces p-nitrophenol to catalysis.Knot
After fruit shows that catalyst is recycled eight times, catalytic reduction reaction to complete required time merely add compared with for the first time
1min, catalytic activity is maintained at more than 90%.Show Fe3O4- rGO-Au catalyst has good stability, and is easily isolated,
It is easy to recycling.
Claims (4)
1. a kind of preparation method for the magnetic noble metal catalyst for strengthening activity with Raman, the catalyst is by the oxidation stone that reduces
Black alkene, noble metal and magnetic Nano material tri compound are formed, and its structure is that magnetic nanoparticle and noble metal are born simultaneously
It is loaded in the surface of the graphene oxide of reduction, the particle diameter of magnetic nanoparticle and noble metal nano particles is respectively 100-4000
Nm and 20-80 nm；Described magnetic Nano material is Fe3O4、MnFe2O4、ZnFe2O4、CoFe2O4In any one, it is described
Noble metal be Au, Ag, Pt, Pd in any one, it is characterised in that：By graphene oxide ultrasonic disperse in ethylene glycol,
Magnetic material precursor is added, after being stirred at room temperature, reactor is transferred to after sequentially adding sodium acetate and polyethylene glycol, stirring,
12-16h is reacted under the conditions of 160-200 DEG C and obtains magnetic-graphene composite material；Reaction is cooled to room temperature after terminating, and uses ethanol
It is centrifuged repeatedly Magneto separate, drying after cleaning；Above-mentioned magnetic-graphene composite material is taken, is dispersed in secondary water, noble metal is added
Precursor solution, is cooled to room temperature, Magneto separate obtains product after being warming up to 90-110 DEG C of reaction 10-20min.
2. the preparation method of the magnetic noble metal catalyst according to claim 1 for strengthening activity with Raman, its feature
It is：Comprise the following steps that：
（1）Graphene oxide is prepared using Hummers oxidizing process；
（2）By graphene oxide ultrasonic disperse in 25mL ethylene glycol, its concentration is controlled in 1mg/mL-5 mg/mL, is then added
0.9-1.8mmol magnetic material precursors, are stirred at room temperature after 1-3h, sequentially add 1.8g sodium acetates and the poly- second two of 0.5g
Alcohol, continues to be transferred to reactor after stirring 0.2-0.8h, 12-16h is reacted under the conditions of 160-200 DEG C, and to obtain magnetic-graphene multiple
Condensation material；Reaction is cooled to room temperature after terminating, and Magneto separate after cleaning is centrifuged repeatedly with ethanol, washes 3-5 times, is placed in vacuum and does
55-65 DEG C of dry 22-26h in dry case；
（3）By step（2）The aqueous dispersions that concentration is 0.5-2mg/mL are made in products obtained therefrom configuration, and addition mass fraction is 1%-
5% noble metal precursor solution 10-200ul, room temperature, Magneto separate are cooled to after being warming up to 95-105 DEG C of reaction 13-17min
Product is obtained, is washed 3-5 times.
3. the preparation method of the magnetic noble metal catalyst according to claim 1 or 2 for strengthening activity with Raman, it is special
Levy and be：Described magnetic material precursor is FeCl3•6H2O, or FeCl3•6H2O and MCl2•nH2O mixture, M be Co,
Any one in Zn, Mn, M2+/Fe3+= 0.5；Described noble metal precursor is water-soluble precious metal salt.
4. described in claim 1 there is Raman to strengthen the catalyst that the preparation method of active magnetic noble metal catalyst is obtained
Purposes, it is characterised in that：The catalyst is used for the reaction for being catalyzed p-nitrophenol and sodium borohydride, while to reactant and instead
Answer product to carry out adsorption and enrichment, and reaction product can also be identified by in-situ Raman spectral detection and anti-to being catalyzed
Process is answered to be tracked.
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| CN105148937A (en) * | 2015-08-07 | 2015-12-16 | 江苏大学 | Magnetic graphene-loaded palladium nano-composite catalyst and preparation method thereof |
| CN105540577B (en) * | 2016-02-26 | 2018-01-30 | 中国科学院理化技术研究所 | A kind of method that room temperature redox graphene prepares graphene and its composite |
| CN105833834B (en) * | 2016-05-13 | 2018-07-10 | 上海应用技术学院 | Reduced graphene/ferroso-ferric oxide/noble metal nano composite material, preparation method and applications |
| TWI631336B (en) * | 2016-06-20 | 2018-08-01 | 明志科技大學 | Magnetic metal two-dimensional nano tablet and manufacturing method thereof |
| 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 |
| CN106541145A (en) * | 2016-10-28 | 2017-03-29 | 四川大学 | A kind of graphene oxide magnetic metal nanowire composite and preparation method thereof |
| CN106925296A (en) * | 2017-03-28 | 2017-07-07 | 青岛科技大学 | A kind of nano composite material and its preparation method and application |
| CN107243344B (en) * | 2017-05-12 | 2020-05-01 | 河南师范大学 | One-step synthesis method of magnetic graphene |
| CN107008456B (en) * | 2017-05-12 | 2020-03-31 | 河南师范大学 | Biologically-assisted synthesis method of photocatalyst with antibacterial performance |
| CN107243348B (en) * | 2017-05-12 | 2020-05-01 | 河南师范大学 | Biologically-assisted synthesis method of antibacterial photocatalyst |
| CN109806876B (en) * | 2018-12-18 | 2022-01-25 | 浙江工业大学 | Magnetic ZnFe2O4Graphene nano composite photocatalyst and preparation method and application thereof |
| CN109626549B (en) * | 2019-01-17 | 2021-11-30 | 上海理工大学 | Method for rapidly catalyzing and degrading 4-nitrophenol |
| CN110064388A (en) * | 2019-05-29 | 2019-07-30 | 黑龙江省科学院石油化学研究院 | A kind of graphene oxide-loaded superfine nano palladium catalyst of N doping and its in-situ preparation method |
| CN116173984A (en) * | 2023-02-13 | 2023-05-30 | 浙江理工大学桐乡研究院有限公司 | Preparation method of manganese ferrite magnetic photocatalyst based on multi-element composite system |
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