CN103007963A - Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier - Google Patents
Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier Download PDFInfo
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Abstract
The invention discloses a method for preparing a bimetallic nanometer alloy composite material by taking graphene as a carrier. The method comprises the following steps of: by taking a precious metal N salt (N=Pd, Pt) and a transition metal M salt (M=Co, Ni and Cu) as precursors and taking graphene oxide as a matrix, reducing the components by employing a reducing agent; and finally, washing, filtering, drying, grinding and roasting to obtain the high-purity graphene bimetallic nanometer composite material. The composite material has high nanoparticle load capacity, stable structure, high uniformity and high dispersing property, has high binding force with the graphene and is high-efficiency in preparation method, low in cost, simple in process and suitable for industrial production. The composite material can be widely applied to the fields of magnetic targeting materials, various catalysts, electromagnetic shielding wave-absorbing materials, super-capacitor electrode materials and other related function materials.
Description
One, technical field
The present invention relates to a kind of composite manufacture method take Graphene as carrier, specifically a kind of preparation method of the bimetal nano alloy composite materials take Graphene as carrier belongs to the nano inorganic material technical field.
Two, background technology
The nano material size is at nanoscale (1～100nm), between microcosmic and macroscopic view, have quantum size effect, small-size effect, surface and interface effect, macro quanta tunnel effect etc. and be different from general properties of materials, for example fusing point, magnetic, optics, heat conduction, conductive characteristic etc., often be different from the character that this material shows when integrality, be widely used in each industrial circles such as metallurgy, coating, material manufacturing, fine chemistry industry.In recent years, increasing researcher begins precious metals pt, Pd nano material are participated in the chemical reaction system as catalyst, improves original harsh reaction condition, so that reaction system becomes gentle, and can improve reaction efficiency.During industrialization technology is used, because the expensive and scarcity of resources of precious metals pt, Pd is subject to the restriction of the many factors such as cost, recovery technology, do not meet the requirement of Green Chemistry.Many studies show that is with noble metal N (N=Pt, Pd) and transition metal M (M=Co, Cu, Ni) alloy material that interacts and prepare is by the cooperative effect between the alloy constituent element, electronic effect, so that alloy material shows stronger chemistry and physical property.
For the preparation of binary nano-alloy crystal, mainly contain mechanical alloying method, reducing process, supercritical ultrasonics technology (claiming again chemical method), pulse electrodeposition method, metal reaction method and liquid phase dispersion method etc.In the method for above-mentioned preparation, mechanical alloy method efficient is not high, and the gained grain diameter is larger, and skewness, and the Nanoalloy of preparing generally is confined to sphere or class is spherical; Supercritical ultrasonics technology is the alloying pellet epigranular of preparing, and better dispersed, but particle is slightly large.Compare above several method, reducing process is a kind of simple and effective method for preparing the Nanoalloy particle.This method at first utilizes suitable reducing agent that metal ion is restored in solvent two kinds of metal salt solutions or metallo-organic compound take redox reaction as the basis, then acts on mutually with dressing agent and prepares the alloying pellet that dressing agent is modified.The particle composition can be controlled by concentration, temperature, reducing agent etc. that the control GOLD FROM PLATING SOLUTION belong to ion, and the Nanoalloy particle of preparation is less, uniform ingredients, and have stronger non-oxidizability.But the Nanoalloy particle causes activity decreased because its larger specific area is very easily reunited in preparation process.Therefore need to find suitable carrier to make the loaded nano double metallic composite material, improve its physical and chemical performance, be beneficial to recycling use, reduce cost.
The structure of carrier and its physicochemical properties, as electric conductivity, specific area etc. can the appreciable impact carrier and metal between interaction, thereby affect the catalytic performance of catalyst.Traditional carrier comprises material with carbon element, Al
2O
3, molecular sieve etc., and material with carbon element (graphite, CNT, active carbon) is compared with other common support materials, has been subject to paying close attention to widely in a plurality of fields.
Graphene is to pass through sp by carbon atom as one of member of charcoal family
2The monolayer honeycomb shape lattice structure that hydridization consists of.Graphene is the elementary cell that consists of other carbon allotropes, and its excellent physical property has attracted more and more researchers' concern.Specific area such as large reaches 2630-2965m
2/ g, high mechanical strength and electric conductivity and stability.Than other material with carbon elements, Graphene has more excellent electron transport ability and large specific area, and low preparation cost, makes it become desirable template and comes the loaded with nano catalyst.Nancy N.Kariuki in 2010 etc. have reported and have selected charcoal load P d-Cu Nanoalloy composite manufacture method (Chem.Mater.2010,22,4144-4152), load to again on the charcoal after must preparing first the Nanoalloy particle in the method, but preparation process is comparatively complicated in preparation alloying pellet process, the size of wayward particle.Therefore how selecting a kind of method simple, with low cost to prepare the catalyst of graphene-supported alloy nano, is the problem that the present invention solves.
Three, summary of the invention
The present invention aims to provide a kind of preparation method of the bimetal nano alloy composite materials take Graphene as carrier, and technical problem to be solved is to improve uniformity and the dispersing uniformity of Nanoalloy particle on carrier of Nanoalloy particle size.
The preparation method of the bimetal nano alloy composite materials of the present invention take Graphene as carrier comprises mixing, reduction, separation, washing, drying, grinds and calcine each unit process:
It is 1g/(100-1000mL that noble metal N salting liquid and transition metal M salting liquid are added concentration) the graphite oxide aqueous solution in and mix, use the lye pH adjustment value〉10 rear adding reducing agents, in 80-100 ℃ of stirring reaction 3-10 hour, centrifugal and washing obtained the black powder to neutral in 60-120 ℃ of drying and after grinding after reaction finished;
Described black powder is placed tube furnace, under inert gas shielding, pass into hydrogen reducing calcining 60-120min in 300-400 ℃, and then under the inertia protection, pass into hydrogen calcining 60-130min in 450-600 ℃, obtain nanometer N-M/ graphene composite material.The present invention adopts two step calcination methods to process, and the first step adopts low temperature calcination, is in order to remove impurity and to be reduced into alloying pellet; Second step adopts high-temperature calcination, and purpose is to improve the crystalline structure of composite.
Described noble metal N salt is the solubility divalent salts of precious metals pd or Pt;
Described transition metal M salt is the solubility divalent salts of transition metal Co, Ni or Cu;
The mol ratio of precious metal element and transition metal is 0.1-10:1 in described noble metal N salt and the described transition metal M salt, and the quality sum of precious metal element and transition metal and the mass ratio of graphene oxide are 1:2-400;
Described reducing agent is selected from sodium borohydride or hydrazine hydrate, and the mass ratio of described sodium borohydride and described graphene oxide is 1:5-10, and described hydrazine hydrate is 20-100mL:1g with the volume mass ratio of described graphene oxide.
Described alkali lye is selected from NaOH solution, KOH solution or ammoniacal liquor.
Described inert gas is selected from nitrogen or argon gas, and the volume ratio of inert gas and hydrogen is 1-10:1.
The flow-control of inert gas is at 0.1-1.0L/min.
The load factor of nanometer N-M/ graphene composite material of the present invention is 0.5-50%, and namely the quality of nanometer N-M particulate load accounts for the percentage of composite gross mass.
The bimetal nano alloy composite materials of the present invention take Graphene as carrier can be noted the graphene composite material as nanometer N-M/ by abridging, and its projection Electronic Speculum (TEM) is presented at the Graphene surface and has deposited more equably nanometer N-M particle, and its average grain diameter is about 10nm.Its X-ray diffraction curve (XRD) demonstration, the purity of the graphene-supported nanometer N-M particle of preparation is higher, does not have other impurity.
The present invention has the advantages such as process is simple, easy to operate, cost is low, prepared alloyed nanocrystal is uniformly dispersed, impurity content is few.
Four, description of drawings
Figure l is nanometer Pd-Co/ graphene composite material (Pd:Co=1:1) the TEM photo of embodiment 1 preparation.As can be seen from Figure 1, deposited more equably the N-M particle on the Graphene surface, its average grain diameter is about 10nm.Particle size range 5-15nm.
Fig. 2 is nanometer Pd-Co/ graphene composite material (Pd:Co=1:1) the EDS photo of embodiment 1 preparation;
Fig. 3 is nanometer Pd-Co/ graphene composite material (Pd:Co=1:1) the XRD figure of embodiment 1 preparation.As can be seen from Figure 3, bimetal nano alloy of the present invention has higher purity.
Five, the specific embodiment
Content of the present invention is further elaborated by following embodiment and accompanying drawing, but does not limit the scope of the invention.
Embodiment 1:
Take by weighing 0.282mmol PdCl
2(AR) and 0.282mmol Co (C
4H
6O
4) 4H
2O (AR), add after mixing and contain in the suspension of 0.3g graphene oxide, 80-90 ℃ of lower magnetic force stirred 1 hour, then slowly added 50mL ammoniacal liquor (AR) and regulated PH〉10, add again the hydrazine hydrate solution of 35mL mass concentration 85%, reaction is 4 hours under the magnetic agitation, after reaction finished, centrifugation obtained black solid, and is extremely neutral with the deionized water washing, then obtain the black chip solid 60 ℃ of lower vacuum drying, will obtain uniform black powder behind the black sheet solid abrasive;
The black powder is tiled on the quartz boat, be placed in the flat-temperature zone of tube furnace, (flow is 600mL/min) is warmed up to 300 ℃ under the nitrogen atmosphere, passes into hydrogen (flow is 100mL/min), reduction calcining 120 minutes is cooled to room temperature under nitrogen (flow the is 600mL/min) protection; (flow is 600mL/min) is warming up to 500 ℃ under nitrogen atmosphere again; pass into hydrogen (flow is 100mL/min) reduction calcining 120 minutes; (flow is 600mL/min) is cooled to room temperature under the nitrogen protection; namely get nanometer Pd-Co/ graphene composite material 123mg; Pd and Co mol ratio are 1:1 in the composite, and the load factor of nanometer Pd-Co particle is 37.8%.
Embodiment 2:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is Pd (C
2H
3O
2)
2(AR), obtain nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=1:1) 124mg, the load factor of nanometer Pd-Co particle is 37.5%.
Embodiment 3:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is Pd (NO
3)
2(AR), obtain nanometer Pd-Co/ graphene composite material (mol ratio Pt:Co=1:1) 134mg, the load factor of nanometer Pd-Co particle is 37.5%.
Embodiment 4:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is PtCl
2(AR), obtain nanometer Pt-Co/ graphene composite material (mol ratio Pt:Co=1:1) 137mg, the load factor of nanometer Pt-Co particle is 46.5%.
Embodiment 5:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.423mmol PdCl
2(AR), transition metal M salt is 0.141mmol Co (C
4H
6O
4) 4H
2O (AR) obtains nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=3:1) 112mg, and the load factor of nanometer Pd-Co particle is 47.5%.
Embodiment 6:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.141mmol PdCl
2(AR), transition metal M salt is 0.423mmol Co (C
4H
6O
4) 4H
2O (AR) obtains nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=1:3) 131mg, and the load factor of nanometer Pd-Co particle is 30.4%.
Embodiment 7:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.282mmol PdCl
2(AR), transition metal M salt is 0.282mmol Ni (NO
3)
26H
2O (AR) obtains nanometer Pd-Ni/ graphene composite material (mol ratio Pd:Ni=1:1) 137mg, and the load factor of nanometer Pd-Ni particle is 37.8%.
Embodiment 8:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.282mmol PdCl
2(AR), transition metal M salt is 0.282mmol CuSO
4(AR), obtain nanometer Pd-Cu/ graphene composite material (mol ratio Pd:Cu=1:1) 137mg, the load factor of nanometer Pd-Cu particle is 34.9%.
Embodiment 9:
The preparation method of the present embodiment is with embodiment 1, and different is, and reducing agent uses is the 50mg sodium borohydride, obtains nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=1:1), and the load factor of nanometer Pd-Co particle is 37.8%.
Claims (4)
1. the preparation method of the bimetal nano alloy composite materials take Graphene as carrier is characterized in that operating according to the following steps:
1) noble metal N salting liquid and transition metal M salting liquid being added concentration is 1g/(100-1000mL) the graphite oxide aqueous solution in and mix, use the lye pH adjustment value〉10 rear adding reducing agents, in 80-100 ℃ of stirring reaction 3-10 hour, centrifugal and washing obtained the black powder to neutral in 60-120 ℃ of drying and after grinding after reaction finished;
2) described black powder is placed tube furnace, under inert gas shielding, pass into hydrogen reducing calcining 60-120min in 300-400 ℃, and then under inertia protection, pass into hydrogen calcining 60-130min in 450-600 ℃, obtain nanometer N-M/ graphene composite material;
Described noble metal N salt is the solubility divalent salts of precious metals pd or Pt;
Described transition metal M salt is the solubility divalent salts of transition metal Co, Ni or Cu;
The mol ratio of precious metal element and transition metal is 0.1-10:1 in described noble metal N salt and the described transition metal M salt, and the quality sum of precious metal element and transition metal and the mass ratio of graphene oxide are 1:2-400;
Described reducing agent is selected from sodium borohydride or hydrazine hydrate, and the mass ratio of described sodium borohydride and described graphene oxide is 1:5-10, and described hydrazine hydrate is 20-100mL:1g with the volume mass ratio of described graphene oxide.
2. preparation method according to claim 1 is characterized in that:
Described alkali lye is selected from NaOH solution, KOH solution or ammoniacal liquor.
3. preparation method according to claim 1 is characterized in that:
Described inert gas is selected from nitrogen or argon gas, and the volume ratio of inert gas and hydrogen is 1-10:1.
4. it is characterized in that according to claim 1 or 3 described preparation methods:
The flow-control of inert gas is at 0.1-1.0L/min.
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