CN102921422A - Preparation of magnetic nano Cu-Fe3O4/grapheme composite catalyst and application of composite catalyst in reduction of nitro-compounds - Google Patents
Preparation of magnetic nano Cu-Fe3O4/grapheme composite catalyst and application of composite catalyst in reduction of nitro-compounds Download PDFInfo
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Abstract
The invention relates to a magnetic nano Cu-Fe3O4/grapheme composite catalyst and application of the composite catalyst in reduction of nitro-compounds. The preparation method comprises the steps of (1) placing graphite oxide into a water soluble alcohol for ultrasonic dispersion; (2) dissolving ferrous salts in water in an ultrasonic mode, then dropwise adding into a solution of Step (1), and mixing uniformly; and (3) dissolving copper salts in water in an ultrasonic mode, adding a sodium hydroxide solution to adjust the pH to be in a range of 10-11, conducting suction filtration and washing to obtain solid products, placing in the water soluble alcohol for ultrasonic dispersion, dripping into a mixing solution of Step (2), mixing uniformly, dropwise adding the sodium hydroxide solution to adjust the pH to be in a range of 10-11, mixing uniformly, and then transferring a mixture system into a hydrothermal still for reaction to obtain the magnetic nano Cu-Fe3O4/grapheme composite catalyst. The preparation method is few in step and simple in process, the prepared composite catalyst can be effectively separated in an applied magnetic field, the problem that the nano catalyst is difficult to recover is solved, and simultaneously, the catalyst has the high catalytic activity in terms of reduction of nitro-compounds.
Description
Technical field
The invention belongs to the magnetic catalyst field, specifically relate to a kind of magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst and the application in nitro compound reducing thereof.
Background technology
Nanocatalyst is owing to its specific surface is large, the Active sites number reaches unique catalytic performance more and gets most of the attention.Yet the nanocatalyst particle diameter is less, is difficult to separate from reaction system by traditional method centrifugal and that filter, and this is so that being recycled into for an engineering difficult point of nanocatalyst limited its application greatly.In recent years, the fast development of nanocatalyst capable of magnetic separating (magnetisable material combines with active component) so that nanocatalyst under externally-applied magnetic field, can be separated, reclaim easyly, and this magnetic nano-catalyst has high activity and easily separated two characteristics concurrently.However, magnetic Nano material is easy to reunite because it can greatly and have magnetic than table, and it is loaded on a kind of good solution of can yet be regarded as on the carrier.Graphene is as a kind of carrier that has more potentiality, and specific area is huge, is present optimal two-dimensional nano material, by widely as the excellent carrier of nano metal particles and metal oxide.
At present, relevant for metal nanoparticle-Fe
3O
4The report of/Graphene heterojunction structure composite manufacture is less, such as: the people such as Li prepare Fe by coprecipitation first
3O
4/ Graphene, the salting liquid with noble metal after the modification of process 1B bridging agent and PVP stabilizing agent reacts, and optionally with Pt, Pd or PtPd nanometer particle load are at Fe
3O
4The surface of/graphene composite material, the good dispersion of nano particle, output high (Chem.Eur.J.2012,18,7601); The employed method of the people such as Hu is prepared first sulfonated graphene (s-G) similarly, then prepares Fe by coprecipitation
3O
4/ s-G, last and palladium salting liquid reaction obtains Pd/Fe
3O
4/ s-G (Catal.Sci.Technol., 2012,2,2332) is by the Pd/Fe of the method preparation
3O
4/ s-G composite can well-proportionedly be dispersed in water or water/ethanol system in.But these class methods prepare metal nanoparticle-Fe
3O
4The step of/graphene composite material is various, and process is complicated, has limited to a certain extent its suitability for industrialized production.Therefore, seek a kind of easy and be easy to the metal-Fe of suitability for industrialized production
3O
4The preparation method of/graphene composite material becomes problem demanding prompt solution.
The present invention directly take graphite oxide and solubility divalent iron salt and mantoquita as raw material, has prepared the magnetic Nano Cu-Fe with high catalytic activity by a step solvent-thermal method under the solvent heat condition
3O
4/ graphene composite catalyst is incited somebody to action the divalent iron salt oxidation of part, thereby has been generated Fe by the oxidation of graphite oxide
3O
4, avoided trivalent iron salt use, saved production cost, Cu, Fe
3O
4With Graphene three's synergy so that this composite has higher catalytic activity, and this preparation method is easy, is easy to suitability for industrialized production.
Summary of the invention
Purpose of the present invention is exactly the deficiency that overcomes background technology, adopts easy method to pass through the nanometer Cu-Fe that the solvent heat process is prepared a kind of novel high catalytic activity and had magnetic concurrently
3O
4/ graphene composite catalyst, and the application of this catalyst in nitro compound reducing is provided.
The technical solution that realizes the object of the invention is that a step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst mainly may further comprise the steps:
(1) graphite oxide is placed the ultrasonic dispersion of water-soluble alcohol;
(2) with the divalent iron salt ultrasonic dissolution in water, then drop in (1) solution, stir;
(3) with the mantoquita ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of water-soluble alcohol, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle to react;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst.
As preferably, the divalent iron salt described in (2) is ferrous sulfate and frerrous chloride.
As preferably, the mantoquita described in (3) is copper nitrate and copper chloride.
As preferably, the water-soluble alcohol described in (1) and (3) is ethanol and ethylene glycol.
As preferably, the mass ratio of mantoquita, divalent iron salt and graphene oxide is (10 ~ 40): (5 ~ 15): 1.
As preferably, the temperature of solvent thermal reaction is 160 ~ 200 ℃ in (3), and the reaction time is 10 ~ 16h.
The present invention compared with prior art, its remarkable advantage:
(1) prepared nanometer Cu-Fe by a step solvent-thermal method
3O
4/ graphene composite catalyst, Cu and Fe
3O
4The generation of nano particle is that method is easy, and does not use trivalent iron salt, utilizes the oxidisability of Graphene to obtain the trivalent iron oxide, and technological operation is easy, has saved production cost;
(2) adopt Graphene as carrier, greatly improved nanometer Cu-Fe
3O
4/ graphene composite catalyst is for the catalytic activity of nitro compound reduction;
(3) this magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst can effectively be separated under externally-applied magnetic field, and it is convenient to recycle.
Description of drawings
Fig. 1 is embodiment 1 obtained magnetic Nano Cu-Fe
3O
4The XRD figure of/graphene composite catalyst.
Fig. 2 is magnetic Nano Cu-Fe of the present invention
3O
4/ graphene composite catalyst preparation method's schematic diagram.
The specific embodiment
Below in conjunction with accompanying drawing invention is described in further detail.
In conjunction with Fig. 2, the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) graphite oxide is placed the ultrasonic dispersion of water-soluble alcohol;
(2) with the divalent iron salt ultrasonic dissolution in water, then drop in (1) solution, stir;
(3) with the mantoquita ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of water-soluble alcohol, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle to react;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst.
Below in conjunction with embodiment the present invention is described in further details.
Embodiment 1: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) take by weighing 0.3025g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in the step (1), stirs 30min;
(3) with 0.9060g copper nitrate ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 200 ℃, reaction 10h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst.TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 35nm.
Fig. 1 is obtained magnetic Nano Cu-Fe
3O
4The XRD figure of/graphene composite catalyst characterizes through X-ray powder diffraction (XRD), and prepared product is Cu-Fe
3O
4, wherein Cu is corresponding to (JCPDS:04-0836), Fe
3O
4Corresponding to (JCPDS:19-0629).
The magnetic Nano Cu-Fe that adopts embodiment 1 to prepare
3O
4/ graphene composite catalyst has very strong catalytic activity for the reduction p-nitrophenol, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into para-aminophenol with 10mL p-nitrophenol (1mmol/L) in 6min, demonstrate excellent catalytic activity.
Embodiment 2: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) take by weighing 0.3528g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.7520g copper nitrate ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 120 ℃, reaction 24h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 26nm.This composite has very strong catalytic activity for the reduction p-nitrophenol, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into para-aminophenol with 10mL p-nitrophenol (1mmol/L) in 16min, demonstrate excellent catalytic activity.
Embodiment 3: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethylene glycol 45min;
(2) take by weighing 0.1895g frerrous chloride ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.3021g copper nitrate ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethylene glycol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 120 ℃, reaction 15h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 32nm.This composite catalyst is not high for the catalytic activity of reduction p-nitrophenol, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into para-aminophenol with 10mL p-nitrophenol (1mmol/L) in 25min.
Embodiment 4: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) take by weighing 0.4295g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.2579g copper chloride ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 250 ℃, reaction 16h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 25nm.This composite catalyst has stronger catalytic activity for the reduction p-nitrophenol, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into para-aminophenol with 10mL p-nitrophenol (1mmol/L) in 20min.
Embodiment 5: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethylene glycol 45min;
(2) take by weighing 0.2845g frerrous chloride ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.2579g copper chloride ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethylene glycol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 250 ℃, reaction 8h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 28nm.This composite catalyst has very strong catalytic activity for the reduction p-nitrophenol, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into para-aminophenol with 10mL p-nitrophenol (1mmol/L) in 14min, demonstrate excellent catalytic activity.
Embodiment 6: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) take by weighing 0.2895g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.7579g copper nitrate ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 120 ℃, reaction 8h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 32nm.This composite catalyst has stronger catalytic activity for the reduction metanitrophenol, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into m-aminophenol with 10mL metanitrophenol (1mmol/L) in 10min, demonstrate excellent catalytic activity.
Embodiment 7: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) take by weighing 0.1545g frerrous chloride ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.3519g copper chloride ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 200 ℃, reaction 16h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 24nm.This composite catalyst has stronger catalytic activity for the reduction o-nitrophenol, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into o-aminophenol with 10mL o-nitrophenol (1mmol/L) in 12min, demonstrate excellent catalytic activity.
Embodiment 8: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) take by weighing 0.1985g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.2579g copper chloride ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 180 ℃, reaction 18h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 35nm.This composite catalyst has stronger catalytic activity for the reduction meta nitro aniline, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into m-phenylene diamine (MPD) with 10mL meta nitro aniline (1mmol/L) in 28min, demonstrate excellent catalytic activity.
Embodiment 9: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL isopropyl alcohol 45min;
(2) take by weighing 0.1985g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.2579g copper chloride ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of isopropyl alcohol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 240 ℃, reaction 10h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 30nm.This composite catalyst has stronger catalytic activity for the reduction parachloronitrobenzene, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into parachloroanilinum with 10mL parachloronitrobenzene (1mmol/L) in 18min, demonstrate excellent catalytic activity.
Embodiment 10: the present invention's one step solvent-thermal method prepares magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) take by weighing 0.1985g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in (1), stirs 30min;
(3) with 0.1975g copper chloride ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 200 ℃, reaction 18h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst, TEM figure shows magnetic Nano Cu-Fe
3O
4Cu-Fe in the/graphene composite catalyst
3O
4Average grain diameter be 24nm.This composite catalyst has preferably catalytic activity for the reduction ortho-methylnitrobenzene, and experimental result shows: in the situation that there is 5mg magnetic Nano Cu-Fe in sodium borohydride
3O
4/ graphene composite catalyst can be catalysed and reduced into ortho-aminotoluene with 10mL ortho-methylnitrobenzene (1mmol/L) in 35min, demonstrate preferably catalytic activity.Reference examples 1: the preparation method of nanometer Cu/ graphene composite catalyst may further comprise the steps:
(1) the 30mg graphite oxide is placed the ultrasonic dispersion of 60mL ethanol 45min;
(2) with 0.9060g copper nitrate ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of ethanol 60min, drop to again in the mixed liquor of (1) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle, 200 ℃, reaction 10h;
(3) product with step (2) filters, and isolates solid product, with deionized water washing, drying, obtains nanometer Cu/ graphene composite catalyst.
The nanometer Cu/ graphene composite catalyst that adopts reference examples 1 to prepare has preferably catalytic activity for the reduction p-nitrophenol, but does not have magnetic, can't realize separating.
Reference examples 2, magnetic Fe
3O
4The preparation method of/graphene composite catalyst may further comprise the steps:
(1) with the step among the embodiment 1 (1);
(2) take by weighing 0.3025g ferrous sulfate ultrasonic dissolution in 5mL water, ultrasonic 15min dropwise drops in the step (1), stirs 30min;
(3) sodium hydroxide solution is dropped in (2), the pH to 10 of adjusting mixed liquor ~ 11 stir, and then place water heating kettle, and 200 ℃, reaction 10h;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Fe
3O
4/ graphene composite catalyst.
The magnetic Fe that adopts reference examples 2 to prepare
3O
4/ graphene composite catalyst has very low catalytic activity for the reduction p-nitrophenol, and experimental result shows: in the situation that there is the 5mg magnetic Fe in sodium borohydride
3O
4/ graphene composite catalyst can not be catalysed and reduced into 10mL p-nitrophenol (1mmol/L) para-aminophenol (reaction is carried out slowlyer) fully within a very long time, show that its catalytic activity is low.
Reference examples 3: in the situation that sodium borohydride exists; the commercial copper powder catalyst of 5mg can not be catalysed and reduced into 10mL p-nitrophenol (1mmol/L) para-aminophenol (reaction is carried out very slowly) fully within a very long time, show that commercial copper powder is very low for the catalytic activity of reduction p-nitrophenol.
With prepared magnetic Nano Cu-Fe
3O
4The catalytic performance of copper catalyst contrasts in/graphene composite catalyst and the document, its result such as table 1.
The made magnetic Nano Cu-Fe of table 1
3O
4The contrast of the catalytic performance of copper catalyst in/graphene composite catalyst and the document
Can find out by table 1, by the magnetic Nano Cu-Fe of solvent-thermal method preparation
3O
4/ graphene composite catalyst is applied to catalyzing N aBH
4In the process of reduction p-nitrophenol para-aminophenol processed, its catalytic activity is apparently higher than the Cu nanosphere of bibliographical information and the catalytic activity of Cu nanometer rods (Catal.Commun., 2010,11,651), magnetic Nano Cu-Fe
3O
4The catalytic activity of/graphene composite catalyst excellence is mainly owing to nanometer Cu, Fe
3O
4And produced cooperative effect between the Graphene three.
Claims (7)
1. magnetic Nano Cu-Fe
3O
4The preparation method of/graphene composite catalyst may further comprise the steps:
(1) graphite oxide is placed the ultrasonic dispersion of water-soluble alcohol;
(2) with the divalent iron salt ultrasonic dissolution in water, then drop in (1) solution, stir;
(3) with the mantoquita ultrasonic dissolution in water, add sodium hydroxide solution and regulate pH to 10 ~ 11, filtering and washing obtains solid product, place the ultrasonic dispersion of water-soluble alcohol, and drop in the mixed liquor of (2) and stir, drip again sodium hydroxide solution and regulate pH to 10 ~ 11, stir, place water heating kettle to react;
(4) product with step (3) carries out the magnetic separation, isolates solid product, and with the deionized water washing, drying obtains magnetic Nano Cu-Fe
3O
4/ graphene composite catalyst.
2. method according to claim 1 is characterized in that, the divalent iron salt described in the step (2) is the water soluble salts such as chloride, nitrate or sulfate of iron.
3. method according to claim 1 is characterized in that, the mantoquita described in the step (3) is the water soluble salts such as chlorination of copper thing, nitrate or sulfate.
4. method according to claim 1 is characterized in that, the water-soluble alcohol described in step (1), (3) can be wherein one or several such as ethanol, ethylene glycol, isopropyl alcohol.
5. described method according to claim 1 is characterized in that, the mass ratio of mantoquita, divalent iron salt and Graphene is (1 ~ 50): (1 ~ 15): 1.
6. method according to claim 1, it is characterized in that: the temperature of solvent thermal reaction is 120 ~ 250 ℃, the time of reaction is 8 ~ 24h.
7. the magnetic Nano Cu-Fe of the described method of claim 1-6 preparation
3O
4The application of/graphene composite catalyst in nitro compound reducing.
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