CN106475131B - A kind of graphene/molecular sieve composite catalyst and preparation method thereof - Google Patents
A kind of graphene/molecular sieve composite catalyst and preparation method thereof Download PDFInfo
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
Abstract
The invention discloses a kind of graphene/molecular sieve composite catalyst and preparation method thereof, which includes graphene and molecular sieve, the quality proportioning of the two are as follows: graphene: 5% ~ 40%；Molecular sieve: 60% ~ 95%；Gained composite material has quasi- two-dimensional slice structure, and the ratio between area and thickness of monolithic layer are greater than 100 microns, and molecular sieve Load Balanced on the surface of graphene, mesoporous diameter is in 2 ~ 30 nm.The preparation method comprises the following steps: graphene, silicon source, silicon source and surfactant are mixed first, containing graphene part is then demultiplex out, then carry out Crystallizing treatment, is finally purified and removed surfactant.Mesoporous graphene/molecular sieves compound material provided by the present invention has the catalytic activity reinforced as solid acid catalyst, for in CBG, EHB reaction, the yield of product can be significantly improved and reusability and do not reduce catalytic activity, had a good application prospect.
Description
Technical field
The present invention relates to a kind of graphene/molecular sieve composite catalysts and preparation method thereof, belong to catalyst and its preparation
Technical field.
Background technique
Molecular sieve catalyst has a wide range of applications in various fields such as industrial petroleum refining, catalysis and separation.ZSM-5 tool
There is three-dimensional network microcellular structure, it is with its unique cellular structure and good catalytic performance, excellent hydrothermal stability and heat
Stability becomes indispensable solid acid catalyst, has good selective activization.However, conventional molecular sieve is all micropore
, 90% aperture is both less than 2nm.There was only 0.5 nm in the aperture of traditional ZSM-5.Since the microcellular structure of molecular sieve leads to molecule
Limited transportation route causes its existing defects in terms of catalytic applications.In addition, the only microcellular structure of traditional ZSM-5, limit
The diffusion of macromolecular substances is made, so that it is difficult to the big molecule of conversion volume.In order to solve this problem, generally by using
Their pore structure of the methods of special structure directing agent, soft template and desiliconization expansion.But these methods make synthesis process
It is complicated, and product is made to become unstable.Contain the molecular sieve of more macropore simultaneously with microcellular structure in catalysis alkane
The extensive concern of people has been caused in base, isomerization, aromatisation, disproportionation, catalytic cracking or condensation reaction.Synthesize one kind
Molecular sieve catalyst has meso-hole structure abundant, while having efficient catalytic efficiency and long service life cycle, this is
It is ideal but also have very big challenge.Graphene is monoatomic layer graphite, is by carbon atom with sp2Hydridization closely connects
The atomic monolayer connect is constituted, and is physically tightly packed real at one kind of bi-dimensional cellular shape lattice structure by single layer of carbon atom
Two-dimensional atomic crystal in meaning has contained abundant and novel physical phenomenon and physical and chemical performance.Due to its special light, electricity,
Heat and mechanical performance, application of the graphene in fields such as photoelectric project, energy storage and electro-catalysis have received widespread attention.
However, up to the present, only only 3 papers reported the compound of graphene and molecular sieve, wherein by pair
The direct charge and discharge of graphite form the less graphene of the number of plies, then compound with titanium-si molecular sieves, have to 4- nitrophenols fine
Photocatalytic activity；Graphene oxide induce large granular silicon dioxide formation, the silica have MFI structure, 2.0 ~ 2.5
Nm is mesoporous, but its catalytic performance has not been reported.The report that in addition, there will be mainly concentrates concern 3D body phase ZSM-5 crystal, arrives mesh
Before until the composite material and its surface acidity of HZSM-5 and graphene have not been reported.
Summary of the invention
The present invention is intended to provide a kind of graphene/molecular sieve composite catalyst, introduces graphite in traditional molecular sieve art
Alkene creatively prepares graphene and molecular sieve binary composite, and aperture changes, and chemical bond is changed, and has
New chemical bond, molecular sieve and graphene have covalent bond and intermolecular force.In addition, the electric conductivity of composite material have it is more
A order of magnitude greatlys improve, so that molecular sieve is applied to electrochemical catalysis and is reacted to possibility.The present invention also provides stones
The preparation method of black alkene/molecular sieve composite catalyst.
The present invention provides a kind of graphene/molecular sieve composite catalyst, including graphene and molecular sieve, the quality of the two
Proportion are as follows:
Graphene: 5% ~ 40%；
Molecular sieve: 60% ~ 95%；
Gained composite material has quasi- two-dimensional slice structure, and the ratio between area and thickness of monolithic layer are greater than 100 microns, point
Son sieves Load Balanced on the surface of graphene, and mesoporous diameter is in 2 ~ 50 nm.
Further, the graphene is one layer of graphene, two layers of graphene, three layers of graphene, multi-layer graphene or oxygen
One of graphite alkene；The molecular sieve is any one of ZSM-5, ZSM-11, SBA-15, MCM, modenite.
Graphene/molecular sieve composite material, electric conductivity average molecular sieve, improves 10000 times or more.Molecular sieve is as two
Silica, it is almost non-conductive, it is insulator.And graphene/molecular sieves compound material electric conductivity is fabulous.Graphene/molecular sieve is multiple
The resistance for closing membrane material can achieve within 100 Ω/squ, and squ is the meaning of square, and Ω/squ is a kind of table of square resistance
Show that method, electric conductivity are 10 order of magnitude multiples of molecular screen membrane.
Graphene/molecular sieve composite material, relative to molecular sieve, the content in mesoporous (apertures of 2 ~ 50 nm) is improved
10 times or more.
Quasi- two-dimensional graphene/molecular sieve composite material, the ratio between area and thickness of monolithic layer are greater than 100 microns, tool
There are catalytic performance and electrocatalysis characteristic.
Graphene/zeolite membrane material, film thickness can control within 20 micron thickness, have the property of catalysis and electro-catalysis
Can, also have the function of seperation film.
Graphene/ZSM-5 composite material, color are black, have the catalytic activity of catalysis macromolecular condensation reaction.Have
Be catalyzed benzaldehyde and the condensation reaction of glycerine, the esterification of caproic acid and benzyl alcohol, the methylation reaction of cyclohexanone, toluene with
The performance of the Benzylation reaction of benzyl chloride and the condensation reaction of benzaldehyde and 2- hydroxy acetophenone, yield is high, has extended cycle life.
Graphene/ZSM-5 composite material has the performance of catalysis benzaldehyde and glycerine condensation reaction, and yield is up to 70%,
Catalyst life is longer than 10 recyclings.
Quasi- two-dimensional ultrathin electric conductivity graphene/molecular screen material, the performance with electro-catalysis and filtering.
The micropore size of ZSM-5 is expanded to 0.7 ± 0.1 nm, and has the mesoporous greater than 10% aperture ratio.
The content of graphene graphene/ZSM-5 composite material between 5 ~ 40% has good acid catalytic property, can show
Write the Bronsted acidic site for improving ZSM-5.
The present invention carries out functional modification to graphene, so that graphene has catalysis and electro catalytic activity position, catalysis
It is very excellent with the performance of electro-catalysis.It is right by the collective effect power of chemical bonding effect and physical absorption to graphene
Graphene has carried out chemistry and physics modification, extends the function of graphene significantly, has expanded the application neck of graphene
Domain.
By means of the present invention, ZSM-5, ZSM-11, SBA-15, MCM, modenite etc. can be loaded on graphene film
The molecular sieve of type prepares the composite material of graphite alkene and molecular sieve.Graphene used in the present invention has one layer, two
Layer, three layers of graphene, there are also multi-layer graphenes, are also possible to graphene oxide, it is possible to obtain different layers of graphenes
With hundreds of graphene of different molecular sieve and the composite material of molecular sieve.The performance difference of different layers of graphenes is larger,
Causing the performance of graphene and molecular sieve also has biggish difference.For example, single-layer graphene has many folds, and three layers of graphene
The performance of rare fold, the composite material of tri- layers of graphene of performance and ZSM-5/ of the composite material of ZSM-5/ single-layer graphene has
A great difference, electric conductivity and heating conduction difference are big.It is raw using the graphene of different layers of graphenes and different lamellas as substrate
The micro-structure of long molecular sieve is also different, can also significantly affect the comprehensive performance of composite material.
The ingredient of binary material of the invention can be regulated and controled by the ratio of raw material.
New material of the invention has micropore and mesoporous micro-structure, the concerted catalysis performance with molecular sieve, graphene, energy
Catalytic molecular alkylation, isomerization, aromatisation, disproportionation, the performance of catalytic cracking or condensation reaction.
The present invention provides a kind of preparation methods of graphene/molecular sieve, comprising the following steps:
Graphene is mixed with molecular sieve predecessor first, containing graphene part is then demultiplex out, next enters crystallization
Processing stage finally enters purifying and surfactant templates removes the stage.
Graphene as described above can with but be not limited to method graphene by electrochemical stripping graphite, it is specific to make
Preparation Method can refer to 103693638 A of Chinese patent CN.
Graphene/molecular sieve predecessor include graphene, the predecessor (silicon source) of silicon and aluminium predecessor (silicon source) and
Surfactant.
Surfactant as described above includes but is not limited to: tetrapropylammonium hydroxide (TPAOH), n-butylamine, tetrem
Base amine and tetrapropyl amine；Source of aluminium choosing includes but is not limited to: aluminium isopropoxide, sodium metaaluminate, waterglass and aluminum sulfate；It is described
Silicon source includes but is not limited to: ethyl orthosilicate, silica solution and sodium metasilicate；Source of aluminium is with Al2O3Meter, the silicon source is with SiO2
Meter.The molar ratio of source of aluminium and silicon source is 1:50 ~ 80；The molar ratio of the template and source of aluminium is 7 ~ 23:1；It is described
Graphene is 5 ~ 40% relative to the mass percent of the sum of silicon source silicon source, i.e. graphene quality/(Al2O3+ SiO2) quality sum
Ratio be 5 ~ 40%.
The template is surfactant.
When source of aluminium is aluminium isopropoxide, the molar ratio of source of aluminium and silicon source is preferably 1:62；
When source of aluminium is sodium metaaluminate, the molar ratio of source of aluminium and silicon source is preferably 1:78.29.
In above-mentioned preparation method, predecessor mixed process includes, but are not limited to: (1) by graphene aqueous solution ultrasound point
It scatters, surface-active template is added thereto and stirs evenly, obtains mixed liquor 1；(2) it is sequentially added into mixed liquor 1 certain
Amount silicon source, silicon source stir evenly, and obtain mixed liquor 2.
Further, include, but are not limited to: mixed liquor 2 is successively carried out to first stage crystallization and second stage is brilliant
Change,
First stage crystalline substance is proceduring are as follows: 80 ~ 90 DEG C of hydro-thermal process；Second stage crystallization process are as follows: 90 ~ 180 DEG C of water
300 ~ 550 DEG C of high-temperature process under heat treatment or anhydrous state.
In above-mentioned preparation method, washed after the removing of template, including but not limited to graphene/molecular sieve predecessor crystallization
Ion exchange is carried out again after washing drying, then air calcination template agent removing, then calcines removing small ion/molecule again.
Wash conditions as described above are the repeated multiple times centrifuge washing of second alcohol and water；Drying temperature is 80 ~ 120 DEG C, and vacuum is dried
Dry 8 ~ 12 h；Template agent removing calcination temperature is 550 ~ 600 DEG C, and the time is 4 ~ 6 h；Calcination temperature after ion exchange is 500 ~
550 DEG C, the time is 4 ~ 6 h；Ion exchange conditions are as follows: calcined graphene/molecular sieves compound material and NH4NO3Exchange,
80 ~ 100 DEG C of stirrings exchange 3 ~ 5 times, exchange 2 ~ 3 h every time；Graphene/molecular sieves compound material and NH4NO3Mass ratio be 1:
2.5~4.5。
Mesoporous graphene/molecular sieves compound material that the present invention is prepared has preferable quasi- 2D lamellar structure, molecule
Load Balanced, better crystallinity degree can regulate and control mesoporous diameter by the quality of simple modulation graphene to sieve on the surface of graphene
In 2 ~ 30 nm.
Above-mentioned mesoporous graphene/molecular sieve composite catalyst the condensation reaction (CBG) of benzaldehyde and glycerine, caproic acid with
The esterification (EHB) of benzyl alcohol, the methylation reaction (OCM) of cyclohexanone, toluene and benzyl chloride it is Benzylation react (BTB) with
And the catalytic applications in the condensation reaction (CBH) of benzaldehyde and 2- hydroxy acetophenone also belong to protection scope of the present invention.
The graphene of electrochemical stripping provides strong interface interaction to the formation of molecular sieve thin layer, and the quasi- 2D is mesoporous
Nano-sheet graphene/molecular sieve has the condensation reaction of the biggish molecule of some volumes such as benzaldehyde and glycerine good
Acidic catalyst effect and the property of can be recycled；The interface induced effect of graphene, make molecular sieve formed meso-hole structure abundant with
And acidic site, and quasi- 2D lamellar structure is formed, which is conducive to the transport of substance.
Beneficial effects of the present invention:
(1) it is quasi- to be capable of providing strong interface interaction induction for the graphene that the present invention is obtained by electrochemical stripping graphite
The formation of 2D molecular sieve, hole size formation, particle size, pattern, mesoporous growth, nucleation, chemistry of the graphene to molecular sieve
Key, surface acidity and stability have strong influence；
(2) present invention has synthesized graphene/molecular sieves compound material of novel 2D a kind of for the first time, and the molecular sieve is mainly to be situated between
Based on hole, while the internal micropore containing 0.7 nm, product of the present invention are a kind of novel catalyst；
(3) mesoporous graphene/molecular sieves compound material provided by the present invention has reinforcement as solid acid catalyst
Catalytic activity, for CBG, EHB reaction in, can significantly improve product yield and reusability and do not reduce catalysis live
Property, it has a good application prospect.
Detailed description of the invention
The optical photograph of Fig. 1 .ZSM-5/ graphene composite material, figure are graphene mass fraction wt% from 0 to 30.
The left side SEM(of Fig. 2 .ZSM-a/ graphene composite material) and the right TEM() picture, figure is graphene mass fraction
The wt% from 0 to 30.
The left side SEM(of Fig. 3 .ZSM-b/ graphene composite material) and the right TEM() picture, figure is graphene mass fraction
The wt% from 0 to 30.
The wide-angle (a) of Fig. 4 .Z5-a and the Z5-a/G sample of different quality containing and low angle (b) XRD.
The wide-angle (a) of Fig. 5 .Z5-b and the Z5-b/G sample of different quality containing and low angle (b) XRD.
Nitrogen suction-the desorption isotherm (a) and pore size distribution (b) of Fig. 6 .Z5-a and Z5-a/G-24 sample.
Nitrogen suction-the desorption isotherm (a) and pore size distribution (b) of Fig. 7 .Z5-b and Z5-b/G-24 sample.
Nitrogen suction-desorption isotherm of Fig. 8 difference graphene content Z5-b/G sample.
(a) XPS and (b) EDS performance of Fig. 9 .Z5-a/G-24 sample.
The NH of Figure 10 .Z5-a, Z5-a/G-24 and Z5-b/G-24 sample3- TPD curve.
Figure 11 .HZSM-a/ graphene composite material is catalyzed benzaldehyde and the recycling performance of glycerine condensation reaction is surveyed
Examination.
Figure 12 .HZSM-b/ graphene composite material is catalyzed the recycling performance test of caproic acid and benzyl alcohol esterification.
Specific embodiment
Specific embodiments of the present invention are described further with reference to the accompanying drawing, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
The Z5-a and Z5-b of comparative example are synthesized according to mode reported in the literature: when silicon source is aluminium isopropoxide, silicon source is positive
Silester, when template is tetrapropyl oxyammonia, each component molar ratio is Al2O3:60SiO2:11.5TPAOH:
1500H2O；When silicon source is sodium metaaluminate, silicon source is ethyl orthosilicate, when template is tetrapropyl oxyammonia (TPAOH), respectively
Component molar ratio is Al2O3:0.00625SiO2:0.25TPAOH:30H2O。
Embodiment 1
The present embodiment prepares mesoporous ZSM-5/ graphene composite material in the following manner, and it is described that its step are as follows.
120 mg graphenes are weighed, 6 ml deionized waters are added, ultrasonic disperse is uniform, weighs 1 g tetrapropyl oxyammonia
It is added in graphene aqueous solution, 30 min of stirring are uniformly mixed, and are denoted as solution A；60 mg isopropyls are sequentially added into solution A
Aluminium alcoholates and 2 ml ethyl orthosilicates stir evenly, and are denoted as B solution；B solution is first then heated to 90 in 30 DEG C of 1 h of stirring
DEG C stirring 24 h；Then polytetrafluoroethyllining lining is transferred to after this B solution ethyl alcohol and deionized water being washed 2 ~ 3 times repeatedly
180 DEG C of 3 d of crystallization of autoclave to get arrive ZSM-a/ graphene composite material.The product passes through ethyl alcohol and deionized water
After washing 3 ~ 5 times, 100 DEG C of 12 h of vacuum drying, 600 DEG C of 5 h of calcining, then with the NH of 0.2 mol/L4NO3Solution is 80
DEG C 6 h of exchange, then washed, dry, calcining is to obtain mesoporous HZSM-a/ graphene composite material.Different graphene contents
The optical photograph of mesoporous HZSM-a/ graphene composite material is shown in that attached drawing 1, SEM and TEM photo are shown in attached drawing 2, and XRD spectra is shown in attached drawing
4, BET the results are shown in attached figure 6 and table 1, and XPS and EDS are shown in attached drawing 9 and table 2, NH3Temperature programmed desorption (NH3- TPD) the result is shown in Figure 10.
HZSM-a is pure white it can be seen from optical photograph, with the increase of graphene content, mesoporous HZSM-a/ stone
The color of black alkene composite material is by light grey gradually blackening；The mesoporous HZSM- being prepared it can be seen from SEM and TEM photo
A/ graphene composite material is quasi- 2D lamellar structure, and HZSM-a uniform load is on the surface of graphene film.
The condensation reaction evaluation that obtained mesoporous HZSM-a/ graphene composite material is carried out to benzaldehyde and glycerine, is urged
Agent quality is 0.1 g, reaction condition are as follows: 0.93 g of glycerine, 1.0 g of benzaldehyde, 5.0 ml of butanol, 0.23 g of hexadecane
As internal standard compound, 70 DEG C of reaction temperature, 6 h of reaction time.The lasting stirring of reaction ensures to be uniformly mixed fully reacting.Experiment knot
Fruit sees attached drawing 11 and table 3.
Embodiment 2
120 mg graphenes are weighed, 8 ml deionized waters are added, ultrasonic disperse is uniform, weighs 2 g tetrapropyl oxyammonias
It is added in graphene aqueous solution, 30 min of stirring are uniformly mixed, and are denoted as solution A；It is inclined that 13.4 mg are sequentially added into solution A
Sodium aluminate and 2 ml ethyl orthosilicates stir evenly, and are denoted as B solution；First by 30 DEG C of B solution 1 h of stirring, 60 DEG C of 2 h of stirring,
80 DEG C of 6 h of stirring are then heated to, poly- four are transferred to after this B solution ethyl alcohol and deionized water are then washed 2 ~ 3 times repeatedly
170 DEG C of 2 d of crystallization of autoclave of vinyl fluoride liner to get arrive ZSM-b/ graphene composite material.The product passes through ethyl alcohol
After being washed 3 ~ 5 times with deionized water, 100 DEG C of 12 h of vacuum drying, 600 DEG C of 5 h of calcining, then with the NH of 0.2 mol/L4NO3
Solution obtains mesoporous HZSM-b/ graphene composite material in 80 DEG C of 6 h of exchange, then washed, dry, calcining.Different graphite
SEM the and TEM photo of the mesoporous HZSM-b/ graphene composite material of alkene content is shown in that attached drawing 3, XRD spectra are shown in attached drawing 5, BET result
See that attached drawing 7 and table 1, XPS and EDS are shown in Table 2.NH3Temperature programmed desorption (NH3- TPD) the result is shown in Figure 10.
The mesoporous HZSM-b/ graphene composite material being prepared it can be seen from SEM and TEM photo is quasi- 2D lamella
Structure, HZSM-b uniform load is on the surface of graphene film.When graphene content is lower than 18%, can see on the surface of graphene
The HZSM-b for seeing discrete particles shape, when graphene content continues growing, HZSM-b becomes tiny spherical nanoparticle, uniformly continuous
Load on the surface of graphene.
The condensation reaction evaluation that obtained mesoporous HZSM-b/ graphene composite material is carried out to benzaldehyde and glycerine, is urged
Agent quality is 0.1 g, reaction condition are as follows: 0.93 g of glycerine, 1.0 g of benzaldehyde, 5.0 ml of butanol, 0.23 g of hexadecane
As internal standard compound, 70 DEG C of reaction temperature, 6 h of reaction time.The lasting stirring of reaction ensures to be uniformly mixed fully reacting.Experiment knot
Fruit is shown in Table 3.
Obtained mesoporous HZSM-b/ graphene composite material is carried out to the esterification evaluation of caproic acid and benzyl alcohol, catalysis
Agent quality is 100 mg, and 1.08 g of benzyl alcohol, 1.16 g of caproic acid, 3.6 g of toluene, 0.23 g of hexadecane is as internal standard compound, instead
Answering temperature is 130 DEG C, and the reaction time is 4 h.The lasting stirring of reaction ensures to be uniformly mixed fully reacting.Experimental result is shown in Figure 12
With table 3.
Embodiment 3
120 mg graphenes are weighed, 6 ml deionized waters are added, ultrasonic disperse is uniform, weighs 3.7 g tetrapropyl hydroxides
Amine is added in graphene aqueous solution, and 30 min of stirring are uniformly mixed, and is denoted as solution A；It is different that 222 mg are sequentially added into solution A
Aluminium propoxide and 7.4 ml ethyl orthosilicates stir evenly, and are denoted as B solution；First B solution is then heated in 30 DEG C of 1 h of stirring
90 DEG C of 24 h of stirring；Then it is transferred in polytetrafluoroethylene (PTFE) after this B solution ethyl alcohol and deionized water being washed 2 ~ 3 times repeatedly
180 DEG C of 3 d of crystallization of autoclave of lining to get arrive ZSM-a/ graphene composite material.The product passes through ethyl alcohol and deionization
After water washing 3 ~ 5 times, 100 DEG C of 12 h of vacuum drying, 600 DEG C of 5 h of calcining, then with the NH of 0.2 mol/L4NO3Solution is 80
DEG C 6 h of exchange, then washed, dry, calcining is to obtain mesoporous HZSM-a/ graphene composite material.Different graphene contents
The optical photograph of mesoporous HZSM-a/ graphene composite material is shown in that attached drawing 1, SEM and TEM photo are shown in attached drawing 2, and XRD spectra is shown in attached drawing
4。
Embodiment 4
120 mg graphenes are weighed, 8 ml deionized waters are added, ultrasonic disperse is uniform, weighs 7.47 g tetrapropyl hydroxides
Amine is added in graphene aqueous solution, and 30 min of stirring are uniformly mixed, and is denoted as solution A；50.03 mg are sequentially added into solution A
Sodium metaaluminate and 7.5 ml ethyl orthosilicates stir evenly, and are denoted as B solution；First by 30 DEG C of B solution 1 h of stirring, 60 DEG C of stirrings 2
H then heats to 80 DEG C of 6 h of stirring, is transferred to after this B solution ethyl alcohol and deionized water are then washed 2 ~ 3 times repeatedly poly-
170 DEG C of 2 d of crystallization of autoclave of tetrafluoroethene liner to get arrive ZSM-b/ graphene composite material.The product passes through second
After pure and mild deionized water is washed 3 ~ 5 times, 100 DEG C of 12 h of vacuum drying, 600 DEG C of 5 h of calcining, then with 0.2 mol/L's
NH4NO3Solution obtains mesoporous HZSM-b/ graphene composite material in 80 DEG C of 6 h of exchange, then washed, dry, calcining.No
SEM and TEM photo with the mesoporous HZSM-b/ graphene composite material of graphene content is shown in that attached drawing 3, XRD spectra are shown in attached drawing 5,
The results are shown in attached figure 8 and table 1 by BET.
Embodiment 5
120 mg graphenes are weighed, 6 ml deionized waters are added, ultrasonic disperse is uniform, weighs 0.74 g tetrapropyl hydrogen-oxygen
Change amine to be added in graphene aqueous solution, 30 min of stirring are uniformly mixed, and are denoted as solution A；44.4 are sequentially added into solution A
Mg aluminium isopropoxide and 1.5 ml ethyl orthosilicates stir evenly, and are denoted as B solution；First then B solution is risen in 30 DEG C of 1 h of stirring
Temperature is to 90 DEG C of 24 h of stirring；Then polytetrafluoroethyl-ne is transferred to after this B solution ethyl alcohol and deionized water being washed 2 ~ 3 times repeatedly
180 DEG C of 3 d of crystallization of autoclave of alkene liner to get arrive ZSM-a/ graphene composite material.The product is by ethyl alcohol and goes
After ion water washing 3 ~ 5 times, 100 DEG C of 12 h of vacuum drying, 600 DEG C of 5 h of calcining, then with the NH of 0.2 mol/L4NO3Solution
Mesoporous HZSM-a/ graphene composite material is obtained in 80 DEG C of 6 h of exchange, then washed, dry, calcining.Different graphenes contain
The optical photograph of the mesoporous HZSM-a/ graphene composite material of amount is shown in that attached drawing 1, SEM and TEM photo are shown in attached drawing 2, and XRD spectra is shown in
Attached drawing 4.
Embodiment 6
120 mg graphenes are weighed, 8 ml deionized waters are added, ultrasonic disperse is uniform, weighs 1.49 g tetrapropyl hydroxides
Amine is added in graphene aqueous solution, and 30 min of stirring are uniformly mixed, and is denoted as solution A；10.0 mg are sequentially added into solution A
Sodium metaaluminate and 1.50 ml ethyl orthosilicates stir evenly, and are denoted as B solution；First by 30 DEG C of B solution 1 h of stirring, 60 DEG C of stirrings
2 h then heat to 80 DEG C of 6 h of stirring, are transferred to after this B solution ethyl alcohol and deionized water are then washed 2 ~ 3 times repeatedly
170 DEG C of 2 d of crystallization of autoclave of polytetrafluoroethyllining lining to get arrive ZSM-b/ graphene composite material.The product passes through
After ethyl alcohol and deionized water are washed 3 ~ 5 times, 100 DEG C of 12 h of vacuum drying, 600 DEG C of 5 h of calcining, then with 0.2 mol/L's
NH4NO3Solution obtains mesoporous HZSM-b/ graphene and answers in 80 DEG C of 6 h of exchange, then washed, dry, 550 DEG C of 5 h of calcining
Condensation material.SEM the and TEM photo of the mesoporous HZSM-b/ graphene composite material of different graphene contents is shown in attached drawing 3, XRD spectra
See attached drawing 5, the results are shown in attached figure 8 and table 1 by BET.
The structural behaviour of the ZSM-5/ graphene composite material of 1. different content graphene of table
The elemental analysis of the ZSM-5/ graphene composite material of 2. different content graphene of table, EDS and XPS result.
The catalytic performance of the ZSM-5/ graphene composite material of 3. different content graphene of table
。
Claims (10)
1. a kind of graphene/molecular sieve composite catalyst, it is characterised in that: including graphene and molecular sieve, the quality of the two is matched
Than are as follows:
Graphene: 5% ~ 40%；
Molecular sieve: 60% ~ 95%；
Gained composite material has quasi- two-dimensional slice structure, and the ratio between area and thickness of monolithic layer are greater than 100 microns, molecular sieve
Load Balanced on the surface of graphene, mesoporous diameter is in 2 ~ 30 nm.
2. graphene/molecular sieve composite catalyst according to claim 1, it is characterised in that: the graphene is one layer
One of graphene, multi-layer graphene or graphene oxide；The molecular sieve is ZSM-5, ZSM-11, SBA-15, MCM, silk
Any one of geolyte.
3. graphene/molecular sieve composite catalyst according to claim 1, it is characterised in that: the molecular sieve is ZSM-5
When, graphene/ZSM-5 composite catalyst color is black, and the micropore size of ZSM-5 is expanded to 0.7 ± 0.1nm, and has
It is mesoporous greater than 10% aperture ratio.
4. a kind of preparation method of the described in any item graphene/molecular sieve composite catalysts of claim 1 ~ 3, feature exist
In: the following steps are included:
Graphene, silicon source, silicon source and surfactant are mixed first, containing graphene part is then demultiplex out, then carry out crystallization
Processing, is finally purified and is removed surfactant；
The surfactant includes: any one of tetrapropylammonium hydroxide, n-butylamine, tetraethyl amine or tetrapropyl amine；Institute
Stating silicon source includes: any one of aluminium isopropoxide, sodium metaaluminate or aluminum sulfate；The silicon source includes: ethyl orthosilicate, silica solution
Any one of with sodium metasilicate.
5. the preparation method of graphene/molecular sieve composite catalyst according to claim 4, it is characterised in that: the aluminium
Source is with Al2O3Meter, the silicon source is with SiO2The molar ratio of meter, source of aluminium and silicon source is 1:50 ~ 80；The surfactant with
The molar ratio of silicon source is 7 ~ 23:1；The graphene is 5 ~ 40% relative to the mass percent of the sum of silicon source silicon source.
6. the preparation method of graphene/molecular sieve composite catalyst according to claim 5, it is characterised in that: the aluminium
When source is aluminium isopropoxide, the molar ratio of source of aluminium and silicon source is 1:62；When source of aluminium is sodium metaaluminate, source of aluminium and silicon
The molar ratio in source is 1:78.29.
7. the preparation method of graphene/molecular sieve composite catalyst according to claim 4, it is characterised in that: described mixed
The concrete operation method of conjunction process are as follows:
(1) graphene aqueous solution ultrasonic disperse is opened, surfactant is added thereto, stirred evenly, obtain mixed liquor 1；
(2) silicon source is sequentially added into mixed liquor 1, silicon source stirs evenly, obtain mixed liquor 2.
8. the preparation method of graphene/molecular sieve composite catalyst according to claim 7, it is characterised in that: further include
Following steps:
Mixed liquor 2 is successively subjected to first stage crystallization and second stage crystallization, first stage crystallization process are as follows: 80 ~ 90 DEG C
Hydro-thermal process；Second stage crystallization process are as follows: 300 ~ 550 DEG C under 90 ~ 180 DEG C of hydro-thermal process or anhydrous state
High-temperature process.
9. the preparation method of graphene/molecular sieve composite catalyst according to claim 4, it is characterised in that: the table
The removing method of face activating agent are as follows: washing and drying after crystallization, air calcination carry out ion exchange after removing surfactant again, then
Removing small ion/molecule is calcined again；Wash conditions are the repeated multiple times centrifuge washing of second alcohol and water；Drying temperature is 80 ~ 120 DEG C,
8 ~ 12 h of vacuum drying；Except surfactant calcination temperature is 550 ~ 600 DEG C, the time is 4 ~ 6 h；Calcining after ion exchange
Temperature is 500 ~ 550 DEG C, and the time is 4 ~ 6 h；Ion exchange conditions are as follows: calcined graphene/molecular sieves compound material with
NH4NO3Exchange exchanges 3 ~ 5 times in 80 ~ 100 DEG C of stirrings, exchanges 2 ~ 3 h every time；Graphene/molecular sieves compound material with
NH4NO3Mass ratio be 1:2.5 ~ 4.5.
10. a kind of described in any item graphene/molecular sieve composite catalysts of claim 1 ~ 3 are in the contracting of benzaldehyde and glycerine
Close reaction, caproic acid and the esterification of benzyl alcohol, the methylation reaction of cyclohexanone, toluene and benzyl chloride it is Benzylation react and
Application in the condensation reaction of benzaldehyde and 2- hydroxy acetophenone.
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