CN104549361A - Magnetic noble metal catalyst with Raman enhanced activity and preparation method of magnetic noble metal catalyst - Google Patents
Magnetic noble metal catalyst with Raman enhanced activity and preparation method of magnetic noble metal catalyst Download PDFInfo
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- CN104549361A CN104549361A CN201410747334.5A CN201410747334A CN104549361A CN 104549361 A CN104549361 A CN 104549361A CN 201410747334 A CN201410747334 A CN 201410747334A CN 104549361 A CN104549361 A CN 104549361A
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Abstract
The invention relates to a magnetic noble metal catalyst with Raman enhanced activity and a preparation method of the magnetic noble metal catalyst. The catalyst is formed by ternary compounding of noble metal, graphene and a magnetic nano material. A preparation method is characterized by comprising the following steps: sequentially depositing iron-based magnetic nano materials including Fe3O4, MnFe2O4, ZnFe2O4 and CoFe2O4 and the like on the surface of graphene oxide in situ, and growing noble metal nano particles including Au, Ag, Pt, Pd and the like. The product provided by the invention has the magnetic responding property of magnetic particles and the operability of an external magnetic field, and efficient adsorption and conductive properties and the like of the graphene nano material, and also has unique optical property and catalytic performance of the noble metal particles; the original Raman enhanced activity and catalytic activity of the noble metal can be enhanced by the synergistic effect between the noble metal nano particles and the graphene material; and the magnetic noble metal catalyst is a magnetic noble metal catalytic material system which can be used for carrying out Raman detection, catalytic reduction degrading and enrichment recycling on low-concentration benzene ring type organic micro-pollutants in water.
Description
Technical field
The invention belongs to nanotechnology, relate to a kind of magnetic noble metal catalyst with Raman enhanced activity and preparation method thereof.
Background technology
INDUSTRIAL ORGANIC POLLUTANTS, especially with aromatic nucleus organic pollutant major part can long-term existence in environment and organism, cause adverse influence to the Sustainable development etc. of ecotope, people ' s health, social safety and economic society, the environmental problem caused thus more and more receives publicity.Wherein, p-NP (4-NP) is a class high toxicity, difficult degradation, be difficult to most administer a compounds, it is the priority pollutants of EPA, the toxic pollutant in Ye Shi China water on priority pollutants Black List.And the toxicity of the reduzate p-aminophenol (4-AP) of 4-NP is relatively much lower, be important chemical industry and medicine intermediate simultaneously.Therefore, the detection of a small amount of 4-NP from solution, enrichment, then to the conversion of 4-AP, detection and recovery, have important practical significance.
Surface enhanced Raman scattering (Surface-enhanced Raman Scattering, SERS) information of the technology molecular level that other detection techniques can be provided to be difficult to obtain, have short, water interference detection time little, do not destroy sample when detecting, do not need to carry out complex process to sample, can the advantage such as direct in-situ analysis, sensing range be wide, the broad interest of scholars is caused in many fields such as bioanalysis and environment pollution detection.As everyone knows, for utilizing NaBH
4the reaction that reduction 4-NP obtains 4-AP could can only occur under the catalysis of the precious metals such as Au, Ag, Pd, and noble metal nano particles is conventional Raman enhancing base material, there is bibliographical information again recently, after precious metal and graphene nano Material cladding, synergistic effect between the two can make the former surface reinforced Raman active that has of nanoparticle and catalytic activity be enhanced.Therefore, for demand mentioned above, we have proposed the solid support material of the mixture of the graphene oxide (rGO) of magnetic nano-particle and reduction as micropollutant process in water, by assembling the noble metal nano particles such as Au, Ag in the further compound in its surface, design and synthesis is simultaneously for the Raman detection of Low Concentration of Benzene lopps organic micro-pollutants in water and the magnetic precious metal catalytic material system of enriching and recovering.
Summary of the invention
The object of the present invention is to provide a kind of magnetic noble metal catalyst with Raman enhanced activity and preparation method thereof.The magnetic noble metal catalyst of Raman enhanced activity that prepared by the method have is made up of the graphene oxide of precious metal, reduction and magnetic Nano material.Its method for making is characterized as successively at the surface in situ deposition Fe of the graphene oxide of reduction
3o
4, MnFe
2o
4, ZnFe
2o
4, CoFe
2o
4deng noble metal nano particles such as iron-base magnetic nano material and growth Au, Ag, Pt, Pd.Matrix material good dispersity in water prepared by the method, can place the several months and not reunite; The mass ratio of precious metal and magnetic nanoparticle and their particle diameter all can by regulating the concentration of reactant to change, and wherein the particle diameter of magnetic and noble metal nano particles can regulate and control respectively between 100-400 and 20-80 nm.
Concrete technical scheme of the present invention is as follows:
The magnetic noble metal catalyst with Raman enhanced activity of the present invention, this matrix material is formed by the graphene oxide reduced, precious metal and magnetic Nano material tri compound, its structure is the surface that magnetic nanoparticle and noble metal are carried on graphene oxide simultaneously, and 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 Fe
3o
4, MnFe
2o
4, ZnFe
2o
4, CoFe
2o
4in any one, described precious metal is any one in Au, Ag, Pt, Pd.
The preparation method with the magnetic noble metal catalyst of Raman enhanced activity of the present invention, by graphene oxide ultrasonic disperse in ethylene glycol, add magneticsubstance precursor, after stirring at room temperature, add sodium-acetate and polyoxyethylene glycol successively, proceed to reactor after stirring, under 160-200 DEG C of condition, react 12-16h obtain magnetic-graphene composite material; Room temperature is cooled to, with Magneto separate, drying after ethanol repeatedly eccentric cleaning after reaction terminates; Get above-mentioned magnetic-graphene composite material, be dispersed in intermediate water, add precious metal precursor solution, be cooled to room temperature after being warming up to 90-110 DEG C of reaction 10-20min, Magneto separate obtains product.
The preparation method with the magnetic noble metal catalyst of Raman enhanced activity of the present invention, concrete steps are as follows:
(1) Hummers oxidation style is adopted to prepare graphene oxide;
(2) by graphene oxide ultrasonic disperse in 25mL ethylene glycol, its concentration controls at 1mg/mL-5 mg/mL, then 0.9-1.8mmol magneticsubstance precursor is added, after stirring at room temperature 1-3h, add 1.8g sodium-acetate and 0.5g polyoxyethylene glycol successively, proceed to reactor after continuing to stir 0.2-0.8h, under 160-200 DEG C of condition, react 12-16h obtain magnetic-graphene composite material; Be cooled to room temperature after reaction terminates, with Magneto separate after ethanol repeatedly eccentric cleaning, wash 3-5 time, be placed in vacuum drying oven 55-65 DEG C of dry 22-26h;
(3) aqueous dispersions that concentration is 0.5-2mg/mL is made in the configuration of step (2) products obtained therefrom, add the precious metal precursor solution 10-200ul that massfraction is 1%-5%, be cooled to room temperature after being warming up to 95-105 DEG C of reaction 13-17min, Magneto separate obtains product, washes 3-5 time.
Described magneticsubstance precursor is FeCl
36H
2o, or FeCl
36H
2o and MCl
2nH
2the mixture of O, M is any one in Co, Ni, Zn, Mn, M
2+/ Fe
3+=0.5; Described precious metal precursor is water-soluble precious metal salt, as the manganate etc. of the nitrate of precious metal, the perchlorate of precious metal and precious metal.
The purposes with the magnetic noble metal catalyst of Raman enhanced activity of the present invention: this catalyzer is used for the reaction of catalysis p-NP and sodium borohydride, adsorption and enrichment can be carried out to reactant and reaction product simultaneously, and can be identified reaction product by in-situ Raman spectral detection and catalytic reaction process be followed the tracks of.
Compared with the magnetic noble metal catalyst of bibliographical information, the magnetic noble metal catalyst with Raman enhanced activity that the present invention proposes has following characteristics: (1) product gathers multi-function in integral whole, magnetic responsiveness and the externally-applied magnetic field both with magnetic-particle are handling, the characteristic such as efficient adsorption, conduction of graphene nano material, there is again optical property and the catalytic performance of noble metal granule uniqueness, a step enrichment of micropollutant in water, highly sensitive detection and Magneto separate can be realized; (2), after precious metal and graphene nano Material cladding, synergistic effect between the two can make the former surface reinforced Raman active that has of nanoparticle and catalytic activity be enhanced, and is expected to the new unit developing sensitiveer and effective detection water Micropollutants; (3) composite nano materials prepared by can modified be strong again, gather multi-function in integral whole, and is conducive to its widespread use in fields such as biomedicine, catalysis, separation.
Accompanying drawing explanation
Fig. 1 is respectively prepared (a) Fe
3o
4-rGO-Au and (b) Fe
3o
4the TEM figure of-rGO-Ag.
Fig. 2 is prepared (a) Fe
3o
4-rGO-Au and (b) Fe
3o
4the XRD collection of illustrative plates of-rGO-Ag.
Fig. 3 is respectively with (a) Fe
3o
4-rGO-Au and (b) Fe
3o
4-rGO-Ag matrix material as catalyzer, NaBH
4the time correlation uv-spectrogram of reduction 4-NP.
Fig. 4 is respectively with (a) Fe
3o
4-rGO-Au and (b) Fe
3o
4-rGO-Ag matrix material as catalyzer, NaBH
4in (the C of reduction 4-NP
0/ C
t) linear relationship chart.
Fig. 5 is with Fe
3o
4-rGO-Au is that catalyzer and Raman strengthen base material, in-site detecting NaBH
4the reaction process Raman spectrogram of reduction 4-NP.
Fig. 6 is Fe
3o
4-rGO-Au (a1) and Fe
3o
4-rGO-Ag (a2) catalyzer mixes with 4-NP solution respectively, after magnetic agitation 30min reaches adsorption equilibrium, and the uv absorption spectra of 4-NP in solution; With Fe
3o
4-rGO-Au (b1) and Fe
3o
4-rGO-Ag (b2) is catalyzer, NaBH
4after reduction 4-NP, Magneto separate, the uv absorption spectra of 4-AP in solution.
Fig. 7 is with Fe
3o
4-rGO-Au is catalyzer, recycles the impact of number of times on catalytic reduction 4-NP.
Embodiment
embodiment 1:
Hummers oxidation style is first adopted to prepare GO.Take 50mg GO, ultrasonic disperse, in 25ml ethylene glycol, adds 0.25g FeCl
36H
2o, after stirring at room temperature 2h, adds 1.8g NaAc and 0.5g PEG successively, proceeds to reactor, under 200 DEG C of conditions, react 16h after continuing to stir 0.5h.Be cooled to room temperature after reaction terminates, with Magneto separate after ethanol repeatedly eccentric cleaning, wash 3 ~ 5 times, be placed in vacuum drying oven 60 DEG C of dry 24h.
Get above-mentioned magnetic-graphene composite material 10mg, by 1mg/mL ultrasonic disperse in 10ml water, add the chlorauric acid solution 100ul that massfraction is 1%, reflux after being warming up to 100 DEG C 15min, and be cooled to room temperature, Magneto separate obtains Fe
3o
4-rGO-Au matrix material, wash 3 ~ 5 times, ultrasonic disperse is in water.
embodiment 2:
Hummers oxidation style is first adopted to prepare GO.Take 50mg GO, ultrasonic disperse, in 25ml ethylene glycol, adds 0.6mmol FeCl
36H
2o and 0.3mmol MnCl
24H
2o, after stirring at room temperature 2h, adds 1.8g NaAc and 0.5g PEG successively, proceeds to reactor, under 200 DEG C of conditions, react 16h after continuing to stir 0.5h.Be cooled to room temperature after reaction terminates, with Magneto separate after ethanol repeatedly eccentric cleaning, wash 3 ~ 5 times, be placed in vacuum drying oven 60 DEG C of dry 24h.
Get above-mentioned magnetic-graphene composite material 10mg, by 1mg/mL ultrasonic disperse in 10ml water, add the chlorauric acid solution 200ul that massfraction is 1%, reflux after being warming up to 100 DEG C 15min, and be cooled to room temperature, Magneto separate obtains MnFe
2o
4-rGO-Au matrix material, wash 3 ~ 5 times, ultrasonic disperse is in water.
embodiment 3:
Hummers oxidation style is first adopted to prepare GO.Take 50mg GO, ultrasonic disperse, in 25ml ethylene glycol, adds 0.9mmol FeCl
36H
2o, after stirring at room temperature 2h, adds 1.8g NaAc and 0.5g PEG successively, proceeds to reactor, under 200 DEG C of conditions, react 16h after continuing to stir 0.5h.Be cooled to room temperature after reaction terminates, with Magneto separate after ethanol repeatedly eccentric cleaning, wash 3 ~ 5 times, be placed in vacuum drying oven 60 DEG C of dry 24h.
Get above-mentioned magnetic-graphene composite material 10mg, by 1mg/mL ultrasonic disperse in 10ml water, add the silver nitrate solution 50ul that massfraction is 1%, reflux after being warming up to 100 DEG C 15min, and be cooled to room temperature, Magneto separate obtains Fe
3o
4-rGO-Ag matrix material, wash 3 ~ 5 times, ultrasonic disperse is in water.
embodiment 4:
Hummers oxidation style is first adopted to prepare GO.Take 50mg GO, ultrasonic disperse, in 25ml ethylene glycol, adds 0.6mmol FeCl
36H
2o and 0.3mmol MnCl
24H
2o, after stirring at room temperature 2h, adds 1.8g NaAc and 0.5g PEG successively, proceeds to reactor, under 200 DEG C of conditions, react 16h after continuing to stir 0.5h.Be cooled to room temperature after reaction terminates, with Magneto separate after ethanol repeatedly eccentric cleaning, wash 3 ~ 5 times, be placed in vacuum drying oven 60 DEG C of dry 24h.
Get above-mentioned magnetic-graphene composite material 10mg, by 1mg/mL ultrasonic disperse in 10ml water, add the silver nitrate solution 100ul that massfraction is 1%, reflux after being warming up to 100 DEG C 15min, and be cooled to room temperature, Magneto separate obtains MnFe
2o
4-rGO-Ag matrix material, wash 3 ~ 5 times, ultrasonic disperse is in water.
The present invention is at previously prepared graphene nano material surface successively in-situ deposition Fe
3o
4, MnFe
2o
4, ZnFe
2o
4, CoFe
2o
4deng noble metal nano particles such as iron-base magnetic nano material and growth Au, Ag, Pt, Pd, obtain a kind of magnetic noble metal catalyst with Raman enhanced activity be made up of the graphene oxide of precious metal, reduction and magnetic Nano material.The size of the magnetic that graphenic surface supports and noble metal nano particles regulates by the amount changing iron-based reactant and precious metal ion.
The magnetic noble metal catalyst good dispersity with Raman enhanced activity adopting above method to prepare, can the several months be placed and not reunite, Graphene presents larger laminated structure, and surface has been covered with magnetic and noble metal nano particles, and particle diameter can regulate and control respectively between 50-400 and 20-80 nm.The specific surface area that Graphene is large, can realize the enrichment of phenyl ring type organic in water; Chemiluminescence between Graphene and noble metal nano particles and the catalytic activity of noble metal nano particles and the SERS signal produced with organic pollutant effect thereof, in conjunction with the inrichment of magnetic-particle and externally-applied magnetic field can be handling, can circulate simultaneously realize Low Concentration of Benzene lopps organic micro-pollutants in water Raman detection, catalytic reduction degraded and enriching and recovering.
From Fe
3o
4-rGO-Au and Fe
3o
4tEM and the SEM photo of-rGO-Ag sample can be found out, Graphene presents larger laminated structure, and surface has been covered with the Fe that particle diameter is about 300nm
3o
4and the Argent grain of the gold of 50nm or 45 nm, and be evenly distributed, without obvious agglomeration.
From Fe
3o
4-rGO-Au and Fe
3o
4the XRD collection of illustrative plates of-rGO-Ag sample can find out, the graphenic surface load magnetic Fe of inverse spinel structure
3o
4nanoparticle and noble metal Au, Ag particle.
From Fe
3o
4-rGO-Au and Fe
3o
4the relevant uv-spectrogram of-rGO-Ag sample catalysis p-NP can draw, when with Fe
3o
4when-rGO-Au matrix material is as catalyzer, the reaction of sodium borohydride reduction p-NP is first order kinetics reaction, and rate constant is 0.500min
-1, when with Fe
3o
4when-rGO-Ag matrix material is as catalyzer, the reaction of sodium borohydride reduction p-NP is also first order kinetics reaction, and rate constant is 0.239min
-1, show superior catalytic performance.
Fig. 5 is with Fe
3o
4-rGO-Au is that catalyzer and Raman strengthen base material, the reaction process Raman spectrogram of in-site detecting sodium borohydride reduction p-NP, spectral line interval 2 min.Under initial state, detect and be positioned at 1345,1113,865 cm
-1for coming from the characteristic peak of p-NP.Along with the carrying out of reaction, nitro is positioned at 1345 cm
-1with 1113 cm
-1vibration performance peak fade away, illustrate that p-NP is progressively reduced, the blob detection of p-aminophenol less than, illustrate p-aminophenol not adsorb by golden nanometer particle.In the process of catalytic reduction, nitro is positioned at 865 cm
-1characteristic peak strengthen gradually, and occurred progressively strengthening be positioned at 852 cm
-1with 1287 cm
-1the nitroso characteristic peak of intermediate product, further demonstrate nitro in catalytic process and first change nitroso-group into, report with document (chemical journal, 2011,69:2368-2372) and match
According to the concentration-absorbance standard curve of Fig. 6 and reactant p-NP and product p-aminophenol, Fe can be obtained
3o
4-rGO-Au and Fe
3o
4-rGO-Ag catalyzer is about 170 mg/g and 148 mg/g respectively to the adsorptive capacity of reactant p-NP, 447 mg/g and 440 mg/g are about respectively to the adsorptive capacity of product p-aminophenol, illustrate that the catalyzer prepared by us can adsorb a certain amount of reactant and product by π-πconjugation, can not secondary pollution be caused.
Fig. 7 is with Fe
3o
4-rGO-Au is catalyzer, recycles the impact of number of times on catalytic reduction p-NP.After result shows that catalyst recirculation uses eight times, catalytic reduction reaction merely add 1min to complete required time compared with first time, and catalytic activity remains on more than 90%.Show Fe
3o
4-rGO-Au catalyzer has satisfactory stability, and is easy to be separated, and is convenient to recycling.
Claims (4)
1. one kind has the magnetic noble metal catalyst of Raman enhanced activity, it is characterized in that: this matrix material is formed by the graphene oxide reduced, precious metal and magnetic Nano material tri compound, its structure is the surface that magnetic nanoparticle and noble metal are carried on the graphene oxide of reduction simultaneously, and 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 Fe
3o
4, MnFe
2o
4, ZnFe
2o
4, CoFe
2o
4in any one, described precious metal is any one in Au, Ag, Pt, Pd.
2. the preparation method with the magnetic noble metal catalyst of Raman enhanced activity according to claim 1, it is characterized in that: by graphene oxide ultrasonic disperse in ethylene glycol, add magneticsubstance precursor, after stirring at room temperature, add sodium-acetate and polyoxyethylene glycol successively, proceed to reactor after stirring, under 160-200 DEG C of condition, react 12-16h obtain magnetic-graphene composite material; Room temperature is cooled to, with Magneto separate, drying after ethanol repeatedly eccentric cleaning after reaction terminates; Get above-mentioned magnetic-graphene composite material, be dispersed in intermediate water, add precious metal precursor solution, be cooled to room temperature after being warming up to 90-110 DEG C of reaction 10-20min, Magneto separate obtains product
The preparation method with the magnetic noble metal catalyst of Raman enhanced activity according to claim 2, is characterized in that: concrete steps are as follows:
(1) Hummers oxidation style is adopted to prepare graphene oxide;
(2) by graphene oxide ultrasonic disperse in 25mL ethylene glycol, its concentration controls at 1mg/mL-5 mg/mL, then 0.9-1.8mmol magneticsubstance precursor is added, after stirring at room temperature 1-3h, add 1.8g sodium-acetate and 0.5g polyoxyethylene glycol successively, proceed to reactor after continuing to stir 0.2-0.8h, under 160-200 DEG C of condition, react 12-16h obtain magnetic-graphene composite material; Be cooled to room temperature after reaction terminates, with Magneto separate after ethanol repeatedly eccentric cleaning, wash 3-5 time, be placed in vacuum drying oven 55-65 DEG C of dry 22-26h;
(3) aqueous dispersions that concentration is 0.5-2mg/mL is made in the configuration of step (2) products obtained therefrom, add the precious metal precursor solution 10-200ul that massfraction is 1%-5%, be cooled to room temperature after being warming up to 95-105 DEG C of reaction 13-17min, Magneto separate obtains product, washes 3-5 time.
3. the preparation method with the magnetic noble metal catalyst of Raman enhanced activity according to Claims 2 or 3, is characterized in that: described magneticsubstance precursor is FeCl
36H
2o, or FeCl
36H
2o and MCl
2nH
2the mixture of O, M is any one in Co, Ni, Zn, Mn, M
2+/ Fe
3+=0.5; Described precious metal precursor is water-soluble precious metal salt, as the manganate etc. of the nitrate of precious metal, the perchlorate of precious metal and precious metal.
4. the purposes with the magnetic noble metal catalyst of Raman enhanced activity as described in claim 1 or 2 or 3, it is characterized in that: this catalyzer is used for the reaction of catalysis p-NP and sodium borohydride, adsorption and enrichment can be carried out to reactant and reaction product simultaneously, and can be identified reaction product by in-situ Raman spectral detection and catalytic reaction process be followed the tracks of.
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