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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
magnetic
noble metal
metal catalyst
precious metal
enhanced activity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410747334.5A
Other languages
Chinese (zh)
Other versions
CN104549361B (en
Inventor
陈凤华
陈庆涛
郑先君
杜俊平
黄海洋
方少明
陈志军
赵涛楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University of Light Industry
Original Assignee
Zhengzhou University of Light Industry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou University of Light Industry filed Critical Zhengzhou University of Light Industry
Priority to CN201410747334.5A priority Critical patent/CN104549361B/en
Publication of CN104549361A publication Critical patent/CN104549361A/en
Application granted granted Critical
Publication of CN104549361B publication Critical patent/CN104549361B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

A kind of magnetic noble metal catalyst with Raman enhanced activity and preparation method thereof
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.
CN201410747334.5A 2014-12-10 2014-12-10 A kind of magnetic noble metal catalyst for strengthening activity with Raman and preparation method thereof Active CN104549361B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410747334.5A CN104549361B (en) 2014-12-10 2014-12-10 A kind of magnetic noble metal catalyst for strengthening activity with Raman and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410747334.5A CN104549361B (en) 2014-12-10 2014-12-10 A kind of magnetic noble metal catalyst for strengthening activity with Raman and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104549361A true CN104549361A (en) 2015-04-29
CN104549361B CN104549361B (en) 2017-11-07

Family

ID=53067066

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410747334.5A Active CN104549361B (en) 2014-12-10 2014-12-10 A kind of magnetic noble metal catalyst for strengthening activity with Raman and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104549361B (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105148937A (en) * 2015-08-07 2015-12-16 江苏大学 Magnetic graphene-loaded palladium nano-composite catalyst and preparation method thereof
CN105540577A (en) * 2016-02-26 2016-05-04 中国科学院理化技术研究所 Method for preparing graphene and graphene composite through reducing graphene oxide at room temperature
CN105833834A (en) * 2016-05-13 2016-08-10 上海应用技术学院 Reduced graphene/ferroferric oxide/precious metal nanocomposite and preparation method and application 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
CN107008456A (en) * 2017-05-12 2017-08-04 河南师范大学 A kind of biological assisted synthesizing method with bacteriostasis property photochemical catalyst
CN107243348A (en) * 2017-05-12 2017-10-13 河南师范大学 A kind of biological assisted synthesizing method of biocidal property photochemical catalyst
CN107243344A (en) * 2017-05-12 2017-10-13 河南师范大学 A kind of one-step method for synthesizing of magnetic graphene
TWI631336B (en) * 2016-06-20 2018-08-01 明志科技大學 Magnetic metal two-dimensional nano tablet and manufacturing method thereof
WO2018176259A1 (en) * 2017-03-28 2018-10-04 青岛科技大学 Nano composite material and preparation method and application thereof
CN109626549A (en) * 2019-01-17 2019-04-16 上海理工大学 A kind of method of quick catalysis degradation 4- nitrophenol
CN109806876A (en) * 2018-12-18 2019-05-28 浙江工业大学 A kind of magnetism ZnFe2O4/ graphene nano composite photo-catalyst and the preparation method and application thereof
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103305185A (en) * 2013-06-08 2013-09-18 西北工业大学 Method for preparing reduced-oxidized graphene/Fe3O4/Ag nano composite wave-absorbing material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103305185A (en) * 2013-06-08 2013-09-18 西北工业大学 Method for preparing reduced-oxidized graphene/Fe3O4/Ag nano composite wave-absorbing material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HUI ZHANG ET AL.: "Graphene Sheets Grafted Ag@AgCI Hybrid with Enhanced Plasmonic Photocatalytic Activity under Visible Light", 《ENVIRONMENTAL SCIENCE&TECHNOLOGY》 *
KOILU ETAL.: "Anomalous magnetic behavior in nanocomposite materials of reduced graphene oxide-Ni/NiFe2O4", 《APPLIED PHYSICS LETTERS》 *
SHIXIN WU ET AL: "Synthesis of Fe3O4 and Pt nanoparticles on reduced graphene oxide and their use as a recyclable catalyst", 《NANOSCALE》 *
郭新立: "石墨烯及其复合材料的制备与应用", 《2014中国功能材料科技与产业高层论坛摘要集》 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105148937A (en) * 2015-08-07 2015-12-16 江苏大学 Magnetic graphene-loaded palladium nano-composite catalyst and preparation method thereof
CN105540577A (en) * 2016-02-26 2016-05-04 中国科学院理化技术研究所 Method for preparing graphene and graphene composite through reducing graphene oxide at room temperature
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
CN105833834A (en) * 2016-05-13 2016-08-10 上海应用技术学院 Reduced graphene/ferroferric oxide/precious metal nanocomposite and preparation method and application thereof
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
WO2018176259A1 (en) * 2017-03-28 2018-10-04 青岛科技大学 Nano composite material and preparation method and application thereof
CN107243344A (en) * 2017-05-12 2017-10-13 河南师范大学 A kind of one-step method for synthesizing of magnetic graphene
CN107243348A (en) * 2017-05-12 2017-10-13 河南师范大学 A kind of biological assisted synthesizing method of biocidal property photochemical catalyst
CN107008456A (en) * 2017-05-12 2017-08-04 河南师范大学 A kind of biological assisted synthesizing method with bacteriostasis property photochemical catalyst
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
CN109806876A (en) * 2018-12-18 2019-05-28 浙江工业大学 A kind of magnetism ZnFe2O4/ graphene nano composite photo-catalyst and the preparation method and application thereof
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
CN109626549A (en) * 2019-01-17 2019-04-16 上海理工大学 A kind of method of quick catalysis degradation 4- nitrophenol
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

Also Published As

Publication number Publication date
CN104549361B (en) 2017-11-07

Similar Documents

Publication Publication Date Title
CN104549361A (en) Magnetic noble metal catalyst with Raman enhanced activity and preparation method of magnetic noble metal catalyst
Karimi-Maleh et al. The role of magnetite/graphene oxide nano-composite as a high-efficiency adsorbent for removal of phenazopyridine residues from water samples, an experimental/theoretical investigation
Wen et al. Photocatalytic degradation of ciprofloxacin by a novel Z-scheme CeO2–Ag/AgBr photocatalyst: influencing factors, possible degradation pathways, and mechanism insight
Ding et al. Conversion of waste eggshell into difunctional Au/CaCO3 nanocomposite for 4-Nitrophenol electrochemical detection and catalytic reduction
He et al. Novel iron (III)-based metal–organic gels with superior catalytic performance toward luminol chemiluminescence
Li et al. A novel peroxidase mimetic Co-MOF enhanced luminol chemiluminescence and its application in glucose sensing
Yan et al. Recent developments of nanoenzyme-based colorimetric sensors for heavy metal detection and the interaction mechanism
Heidari-Asil et al. Amino acid assisted-synthesis and characterization of magnetically retrievable ZnCo2O4–Co3O4 nanostructures as high activity visible-light-driven photocatalyst
Bhat et al. Highly efficient catalytic reductive degradation of Rhodamine-B over Palladium-reduced graphene oxide nanocomposite
Huang et al. Electrochemical monitoring of persistent toxic substances using metal oxide and its composite nanomaterials: Design, preparation, and application
Xu et al. Microbial synthesis of Pd–Pt alloy nanoparticles using Shewanella oneidensis MR-1 with enhanced catalytic activity for nitrophenol and azo dyes reduction
Chen et al. A facile preparation method for efficiency a novel LaNiO3/SrCeO3 (pn type) heterojunction catalyst in photocatalytic activities, bactericidal assessment and dopamine detection
Zhao et al. Recent advances in metal organic frame photocatalysts for environment and energy applications
Purbia et al. Green synthesis of single-crystalline akaganeite nanorods for peroxidase mimic colorimetric sensing of ultralow-level vitamin B1 and sulfide ions
Sobhanardakani et al. Cerium dioxide nanoparticles decorated on CuFe2O4 nanofibers as an effective adsorbent for removal of estrogenic contaminants (bisphenol A and 17-α ethinylestradiol) from water
Jing et al. Porous boron nitride micro-nanotubes efficiently anchor CoFe2O4 as a magnetic recyclable catalyst for peroxymonosulfate activation and oxytetracycline rapid degradation
Cong et al. A dandelion-like NiCo2O4 microsphere with superior catalytic activity as the mediator of persulfate activation for high-efficiency degradation of emerging contaminants
Mirbagheri et al. Magnetic ethyl-based organosilica supported Schiff-base/indium: A very efficient and highly durable nanocatalyst
Wang et al. Spinel-oxide-based laccase mimics for the identification and differentiation of phenolic pollutants
Zhang et al. Ultrathin binary MOF nanozyme with boosted activity via introduction of active iron sites for detecting sulfide ion
Liang et al. Promoting sensitive colorimetric detection of hydroquinone and Hg2+ via ZIF-8 dispersion enhanced oxidase-mimicking activity of MnO2 nanozyme
Xiang et al. Efficient degradation of methylene blue by magnetically separable Fe3O4/chitosan/TiO2 nanocomposites
Fu et al. Regulating crystal facets of MnO2 for enhancing peroxymonosulfate activation to degrade pollutants: performance and mechanism
Vinoth et al. Detection of the neurodegenerative drug in a biological sample using three-dimensional sphere mixed metal oxide tailored with carbon fiber as an electrocatalyst by voltammetry technique
Cui et al. Recent advances in luminescence and aptamer sensors based analytical determination, adsorptive removal, degradation of the tetracycline antibiotics, an overview and outlook

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant