CN106475131A - 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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- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
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Abstract
The invention discloses a kind of Graphene/molecular sieve composite catalyst and preparation method thereof, this composite catalyst includes Graphene and molecular sieve, and the quality proportioning of the two is：Graphene：5%~40%；Molecular sieve：60%~95%；Gained composite has quasi- two-dimensional slice structure, and the area of monolithic layer is more than 100 microns with the ratio of thickness, and, in graphenic surface Load Balanced, mesoporous diameter is in 2 ~ 30 nm for molecular sieve.Preparation method is：First Graphene, silicon source, silicon source and surfactant are mixed, be then demultiplex out graphene-containing part, then carry out Crystallizing treatment, finally carry out purification and remove surfactant.Mesoporous Graphene/molecular sieves compound material provided by the present invention has the catalysis activity of reinforcement as solid acid catalyst, for in CBG, EHB reaction, the yield of product and reusability can be significantly improved and do not reduce catalysis activity, there is good application prospect.
Description
Technical field
The present invention relates to a kind of Graphene/molecular sieve composite catalyst and preparation method thereof, belong to catalyst and its preparation
Technical field.
Background technology
Molecular sieve catalyst has a wide range of applications in various fields such as industrial petroleum refining, catalysis and separation.ZSM-5 has
There is three-dimensional network microcellular structure, it is with its unique pore passage 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.The aperture of traditional ZSM-5 only has 0.5 nm.Microcellular structure due to molecular sieve leads to molecule
Limited transportation route, causes its existing defects in terms of catalytic applications.Additionally, the only microcellular structure of traditional ZSM-5, limit
The diffusion having made macromolecular substances is so that it is difficult to the big molecule of conversion volume.In order to solve this problem, typically by using
The methods such as special structure directing agent, soft template and desiliconization expand their pore structure.But, these methods make building-up process
Complicated, and make product become unstable.There is microcellular structure and contain the molecular sieve of more macropore in catalysis alkane simultaneously
The extensive concern of people has been caused in base, isomerization, aromatisation, disproportionation, catalytic cracking or condensation reaction.Synthesis is a kind of
Molecular sieve catalyst has abundant meso-hole structure, has efficient catalytic efficiency and long service life cycle, this is simultaneously
Ideal but also there is very big challenge.Graphene is monoatomic layer graphite, is with sp by carbon atom2Hydridization closely connects
The atomic monolayer connecing is constituted, and is physically a kind of real by monolayer carbon atom tightly packed one-tenth bi-dimensional cellular shape lattice structure
Two-dimensional atomic crystal in meaning, has contained and has enriched and the physical phenomenon of novelty and physical and chemical performance.Due to its special light, electricity,
Heat and mechanical performance, the application in fields such as photoelectric project, energy storage and electro-catalysis for the Graphene receives extensive concern.
However, up to the present, only only 3 papers reported the compound of Graphene and molecular sieve, and it is right wherein to pass through
The direct discharge and recharge of graphite forms the less Graphene of the number of plies, is then combined with titanium-si molecular sieves, 4- nitrophenols are had very well
Photocatalytic activity；Graphene oxide induces the formation of large granular silicon dioxide, and this silicon dioxide has MFI structure, and 2.0 ~ 2.5
Nm is mesoporous, but its catalytic performance has no report.The report that in addition, there will be mainly concentrates concern 3D body phase ZSM-5 crystal, to mesh
Before till the composite of HZSM-5 and Graphene and its surface acidity have no report.
Content of the invention
The present invention is intended to provide a kind of Graphene/molecular sieve composite catalyst, introduce graphite in traditional molecular sieve art
Alkene, creatively prepares Graphene and molecular sieve binary composite, and aperture changes, and chemical bond there occurs change, has
New chemical bond, molecular sieve and Graphene have covalent bond and an intermolecular force.In addition, the electric conductivity of composite have many
Being greatly enhanced so that molecular sieve is applied to electrochemical catalysis is reacted to possibility of the individual order of magnitude.Present invention also offers stone
The preparation method of black alkene/molecular sieve composite catalyst.
The invention provides a kind of Graphene/molecular sieve composite catalyst, including Graphene and molecular sieve, the quality of the two
Proportioning is：
Graphene：5%~40%；
Molecular sieve：60%~95%；
Gained composite has quasi- two-dimensional slice structure, and the area of monolithic layer is more than 100 microns with the ratio of thickness, molecular sieve
In graphenic surface Load Balanced, mesoporous diameter is in 2 ~ 50 nm.
Further, described Graphene is a layer graphene, two layer graphenes, three layer graphenes, multi-layer graphene or oxygen
One of graphite alkene；Described molecular sieve is ZSM-5, ZSM-11, SBA-15, MCM, any one in modenite.
Graphene/molecular sieve composite material, electric conductivity average molecular sieves, and improves more than 10000 times.Molecular sieve is as two
Silicon oxide, almost non-conductive, it is insulator.And Graphene/molecular sieves compound material electric conductivity is fabulous.Graphene/molecular sieve is multiple
Within the resistance of conjunction membrane material can reach 100 Ω/squ, squ is the meaning of square, and Ω/squ is a kind of table of square resistance
Show method, electric conductivity is 10 order of magnitude multiples of molecular screen membrane.
Graphene/molecular sieve composite material, with respect to molecular sieve, mesoporous（The aperture of 2 ~ 50 nm）Content improve
More than 10 times.
Graphene/molecular sieve the composite material of quasi- two dimension, the area of monolithic layer is more than 100 microns with the ratio of thickness, tool
There are catalytic performance and electrocatalysis characteristic.
Graphene/zeolite membrane material, film thickness can control within 20 micron thickness, has the property of catalysis and electro-catalysis
Can, also there is the function of seperation film.
Graphene/ZSM-5 composite, color is black, has the catalysis activity of catalysis macromole condensation reaction.Have
The esterification of condensation reaction, caproic acid and benzyl alcohol of catalysis benzaldehyde and glycerol, the methylation reaction of Ketohexamethylene, toluene with
The performance of the condensation reaction of the Benzylation reaction of benzyl chloride and benzaldehyde and 2- hydroxy acetophenone, yield is high, has extended cycle life.
Graphene/ZSM-5 composite has the performance of catalysis benzaldehyde and glycerol 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, has electro-catalysis and the performance filtering.
The micropore size of ZSM-5 expands 0.7 ± 0.1 nm to, and has the mesopore more than 10% aperture ratio.
The content of Graphene Graphene/ZSM-5 composite between 5 ~ 40%, has good acid catalytic property, can show
Write the Bronsted acidic site improving ZSM-5.
The present invention carries out functional modification to Graphene so that Graphene possesses catalysis and electro catalytic activity position, catalysis
Very excellent with the performance of electro-catalysis.By to the chemical bonding effect of Graphene and the collective effect power of physical absorption, right
Graphene has carried out chemistry and physics modification, significantly extends the function of Graphene, has expanded the application neck of Graphene
Domain.
By the method for 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 of graphite alkene and molecular sieve.Graphene used by the present invention have one layer, two
Layer, three layer graphenes, also multi-layer graphene or graphene oxide are it is possible to obtain the Graphene of the different numbers of plies
With hundreds of Graphene of different molecular sieve and the composite of molecular sieve.The performance difference of the Graphene of the different numbers of plies is larger,
Graphene and the performance of molecular sieve is caused also to have larger difference.For example, single-layer graphene has a lot of folds, and three layer graphenes
Rare fold, the performance of the composite of ZSM-5/ single-layer graphene is had with the performance of the composite of ZSM-5/ tri- layer graphene
A great difference, electric conductivity and heat conductivility difference are big.With the Graphene of the Graphene of the different numbers of plies and different lamella as substrate, raw
The micro structure of long molecular sieve is also different, also can appreciable impact composite combination property.
The composition of the binary material of the present invention can be regulated and controled by the ratio of raw material.
The new material of the present invention has micropore and mesoporous micro structure, has the concerted catalysis performance of molecular sieve, Graphene, energy
The performance of catalytic molecular alkylation, isomerization, aromatisation, disproportionation, catalytic cracking or condensation reaction.
The invention provides a kind of preparation method of Graphene/molecular sieve, comprise the following steps：
First Graphene is mixed with molecular sieve predecessor, be then demultiplex out graphene-containing part, next enter Crystallizing treatment
In the stage, finally enter purification and surfactant templates remove the stage.
Graphene as above can but be not limited to the method Graphene by electrochemical stripping graphite, concrete system
Preparation Method refers to Chinese patent CN 103693638 A.
The predecessor of Graphene/molecular sieve includes the predecessor of Graphene, silicon（Silicon source）Predecessor with aluminum（Silicon source）With
Surfactant.
Surfactant as above includes but is not limited to：TPAOH（TPAOH）, n-butylamine, tetrem
Base amine and tetrapropyl amine；Source of aluminium choosing includes but is not limited to：Aluminum isopropylate., sodium metaaluminate, waterglass and aluminum sulfate；Described
Silicon source includes but is not limited to：Tetraethyl orthosilicate, Ludox and sodium silicate；Source of aluminium is with Al2O3Meter, described silicon source is with SiO2
Meter.Source of aluminium is 1 with the mol ratio of silicon source:50~80；Described template is 7 ~ 23 with the mol ratio of source of aluminium:1；Described
Graphene with respect to silicon source silicon source sum mass percent be 5 ~ 40%, that is, Graphene quality/（Al2O3+ SiO2）Quality sum
Ratio be 5 ~ 40%.
Described template is surfactant.
When source of aluminium is aluminum isopropylate., source of aluminium is preferably 1 with the mol ratio of silicon source:62；
When source of aluminium is sodium metaaluminate, source of aluminium is preferably 1 with the mol ratio of silicon source:78.29.
In above-mentioned preparation method, predecessor mixed process includes, but are not limited to：（1）By ultrasonic for graphene aqueous solution point
Scatter, be added thereto to surface activity template and stir, obtain mixed liquor 1；（2）Sequentially add certain in mixed liquor 1
Amount silicon source, silicon source stir, and obtain mixed liquor 2.
Further, include, but are not limited to：Mixed liquor 2 is carried out successively first stage crystallization and second stage is brilliant
Change,
First stage crystalline substance process turns to：80 ~ 90 DEG C of hydrothermal treatment consists；Second stage crystallization process is：At 90 ~ 180 DEG C of hydro-thermal
Reason, or 300 ~ 550 DEG C of high-temperature process under anhydrous state.
In above-mentioned preparation method, wash after the removing of template, including but not limited to Graphene/molecular sieve predecessor crystallization
Wash drying, then after air calcination template agent removing, carry out ion exchange again, then calcine removing small ion/molecule again.
Condition washed described above is 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 calcining heat is 550 ~ 600 DEG C, and the time is 4 ~ 6 h；Calcining heat after ion exchange be 500 ~
550 DEG C, the time is 4 ~ 6 h；Ion exchange conditions are：Graphene/molecular sieves compound material after calcining and NH4NO3Exchange,
80 ~ 100 DEG C are stirred 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 prepares has preferably quasi- 2D lamellar structure, molecule
Sieve, in graphenic surface Load Balanced, better crystallinity degree, by the quality of simple modulation Graphene, can regulate and control mesoporous diameter
In 2 ~ 30 nm.
Above-mentioned mesoporous Graphene/molecular sieve composite catalyst is in the condensation reaction of benzaldehyde and glycerol（CBG）, caproic acid with
The esterification of benzyl alcohol（EHB）, the methylation reaction of Ketohexamethylene（OCM）, the Benzylation reaction of toluene and benzyl chloride（BTB）With
And the condensation reaction of benzaldehyde and 2- hydroxy acetophenone（CBH）In catalytic applications fall within protection scope of the present invention.
The Graphene of electrochemical stripping provides strong interface interaction to the formation of molecular sieve thin layer, and this quasi- 2D is mesoporous
The condensation reaction of nano-sheet Graphene/molecular sieve the molecule such as benzaldehyde and glycerol larger to some volumes has well
Acidic catalyst effect and the property of can be recycled；The interface induced effect of Graphene, make molecular sieve formed abundant meso-hole structure with
And acidic site, and forming quasi- 2D lamellar structure, this lamellar structure is conducive to the transport of material.
Beneficial effects of the present invention：
（1）The Graphene that the present invention is obtained by electrochemical stripping graphite, using the teaching of the invention it is possible to provide strong interface interaction induces quasi- 2D to divide
The formation of son sieve, Graphene is to the hole size formation of molecular sieve, size, pattern, mesoporous growth, nucleation, chemical bond, acid
Catalysis activity and stability have strong influence；
（2）The present invention has synthesized a kind of Graphene/molecular sieves compound material of new 2D first, and this molecular sieve with mesoporous is mainly
Main, the internal micropore containing 0.7 nm simultaneously, product of the present invention is a kind of new catalyst；
（3）Mesoporous Graphene/molecular sieves compound material provided by the present invention has the catalysis of reinforcement as solid acid catalyst
Activity, for, in CBG, EHB reaction, the yield of product and reusability can be significantly improved and do not reduce catalysis activity, tool
There is good application prospect.
Brief description
The optical photograph of Fig. 1 .ZSM-5/ graphene composite material, figure is Graphene mass fraction from 0 to 30 wt%.
The SEM of Fig. 2 .ZSM-a/ graphene composite material（The left side）And TEM（The right）Picture, figure is Graphene mass fraction
From 0 to 30 wt%.
The SEM of Fig. 3 .ZSM-b/ graphene composite material（The left side）And TEM（The right）Picture, figure is Graphene mass fraction
From 0 to 30 wt%.
The Radix Rumiciss (a) of Z5-a/G sample of Fig. 4 .Z5-a and different quality containing and low angle (b) XRD.
The Radix Rumiciss (a) of Z5-b/G sample of Fig. 5 .Z5-b and different quality containing and low angle (b) XRD.
Nitrogen suction-desorption isotherm (a) of Fig. 6 .Z5-a and Z5-a/G-24 sample and pore size distribution (b).
Nitrogen suction-desorption isotherm (a) of Fig. 7 .Z5-b and Z5-b/G-24 sample and pore size distribution (b).
Fig. 8. the nitrogen suction-desorption isotherm of different Graphene content Z5-b/G samples.
(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 glycerol 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
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described further, but the invention is not limited in this.
Experimental technique used in following embodiments if no special instructions, is conventional method；Institute in following embodiments
Reagent, material etc., if no special instructions, all commercially obtain.
Z5-a and Z5-b of comparative example is to synthesize according to the mode of document report：When silicon source is aluminum isopropylate., silicon source is just
Silester, when template is tetrapropyl oxyammonia, each component molar ratio is for Al2O3:60SiO2:11.5TPAOH:
1500H2O；When silicon source is sodium metaaluminate, silicon source is tetraethyl orthosilicate, and template is tetrapropyl oxyammonia（TPAOH）When, respectively
Component molar is than for Al2O3:0.00625SiO2:0.25TPAOH:30H2O.
Embodiment 1
The present embodiment prepares mesoporous ZSM-5/ graphene composite material in the following manner, and its step is as described below.
Weigh 120 mg Graphenes, add 6 ml deionized waters, ultrasonic disperse uniformly, weighs 1 g tetrapropyl oxyammonia
It is added in graphene aqueous solution, stir 30 min mix homogeneously, be designated as solution A；60 mg isopropyls are sequentially added in solution A
Aluminium alcoholates and 2 ml tetraethyl orthosilicates stir, and are designated as B solution；First B solution is stirred 1 h at 30 DEG C, then heat to 90
DEG C stirring 24 h；Then it is transferred to polytetrafluoroethyllining lining by after this B solution ethanol and deionized water cyclic washing 2 ~ 3 times
180 DEG C of crystallization 3 d of autoclave, that is, obtain ZSM-a/ graphene composite material.This product is through ethanol and deionized water
After washing 3 ~ 5 times, 100 DEG C of vacuum drying 12 h, 600 DEG C of calcining 5 h, then with the NH of 0.2 mol/L4NO3Solution is 80
DEG C exchange 6 h, more scrubbed, drys, calcine obtain mesoporous HZSM-a/ graphene composite material.Different Graphene contents
The optical photograph of mesoporous HZSM-a/ graphene composite material is shown in accompanying drawing 1, and accompanying drawing 2 is shown in by SEM and TEM photo, and XRD spectra is shown in accompanying drawing
4, BET results are shown in accompanying drawing 6 and table 1, XPS and EDS is shown in accompanying drawing 9 and table 2, NH3Temperature programmed desorption（NH3-TPD）Result is shown in Figure 10.
By optical photograph as can be seen that HZSM-a is pure white, with the increase of Graphene content, mesoporous HZSM-a/ stone
The color of black alkene composite is by light gray gradually blackening；Can be seen that the mesoporous HZSM- preparing by 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 mesoporous HZSM-a/ graphene composite material obtaining is carried out the condensation reaction evaluation of benzaldehyde and glycerol, urge
Agent quality is 0.1 g, and reaction condition is：Glycerol 0.93 g, benzaldehyde 1.0 g, butanol 5.0 ml, hexadecane 0.23 g
As internal standard substance, 70 DEG C of reaction temperature, response time 6 h.Reaction is continuously stirred to guarantee mix homogeneously reaction completely.Experiment knot
Fruit sees accompanying drawing 11 and table 3.
Embodiment 2
Weigh 120 mg Graphenes, add 8 ml deionized waters, ultrasonic disperse uniformly, weighs 2 g tetrapropyl oxyammonias and adds
To in graphene aqueous solution, stir 30 min mix homogeneously, be designated as solution A；13.4 mg meta-aluminic acids are sequentially added in solution A
Sodium and 2 ml tetraethyl orthosilicates stir, and are designated as B solution；First by 30 DEG C of stirring 1 h of B solution, 60 DEG C of stirring 2 h, then
It is warming up to 80 DEG C of stirring 6 h, be then transferred to polytetrafluoroethyl-ne by after this B solution ethanol and deionized water cyclic washing 2 ~ 3 times
170 DEG C of crystallization 2 d of the autoclave of alkene liner, that is, obtain ZSM-b/ graphene composite material.This product through ethanol and goes
After ion water washing 3 ~ 5 times, 100 DEG C of vacuum drying 12 h, 600 DEG C of calcining 5 h, then with the NH of 0.2 mol/L4NO3Solution
In 80 DEG C of exchange 6 h more scrubbed, dry, calcining obtains mesoporous HZSM-b/ graphene composite material.Different Graphenes contain
Accompanying drawing 3 is shown in by SEM the and TEM photo of the mesoporous HZSM-b/ graphene composite material of amount, and XRD spectra is shown in accompanying drawing 5, and BET result is shown in attached
Fig. 7 and Biao 1, XPS and EDS is shown in Table 2.NH3Temperature programmed desorption（NH3-TPD）Result is shown in Figure 10.
Be can be seen that the mesoporous HZSM-b/ graphene composite material preparing by SEM and TEM photo be quasi- 2D lamella
Structure, HZSM-b uniform load is on the surface of graphene film.When Graphene content is less than 18%, can see in graphenic surface
See the HZSM-b of discrete particles shape, when Graphene content continues to increase, HZSM-b becomes tiny spherical nanoparticle, uniformly continuous
Be supported on graphenic surface.
The mesoporous HZSM-b/ graphene composite material obtaining is carried out the condensation reaction evaluation of benzaldehyde and glycerol, urge
Agent quality is 0.1 g, and reaction condition is：Glycerol 0.93 g, benzaldehyde 1.0 g, butanol 5.0 ml, hexadecane 0.23 g
As internal standard substance, 70 DEG C of reaction temperature, response time 6 h.Reaction is continuously stirred to guarantee mix homogeneously reaction completely.Experiment knot
Fruit is shown in Table 3.
The mesoporous HZSM-b/ graphene composite material obtaining is carried out the esterification evaluation of caproic acid and benzyl alcohol, catalysis
Agent quality is 100 mg, benzyl alcohol 1.08 g, caproic acid 1.16 g, toluene 3.6 g, hexadecane 0.23 g as internal standard substance, instead
Temperature is answered to be 130 DEG C, the response time is 4 h.Reaction is continuously stirred to guarantee mix homogeneously reaction completely.Experimental result is shown in Figure 12
With table 3.
Embodiment 3
Weigh 120 mg Graphenes, add 6 ml deionized waters, ultrasonic disperse uniformly, weighs 3.7 g tetrapropyl oxyammonias and adds
Enter in graphene aqueous solution, stir 30 min mix homogeneously, be designated as solution A；222 mg isopropanols are sequentially added in solution A
Aluminum and 7.4 ml tetraethyl orthosilicates stir, and are designated as B solution；First B solution is stirred 1 h at 30 DEG C, then heat to 90
DEG C stirring 24 h；Then it is transferred to polytetrafluoroethyllining lining by after this B solution ethanol and deionized water cyclic washing 2 ~ 3 times
180 DEG C of crystallization 3 d of autoclave, that is, obtain ZSM-a/ graphene composite material.This product is through ethanol and deionized water
After washing 3 ~ 5 times, 100 DEG C of vacuum drying 12 h, 600 DEG C of calcining 5 h, then with the NH of 0.2 mol/L4NO3Solution is 80
DEG C exchange 6 h, more scrubbed, drys, calcine obtain mesoporous HZSM-a/ graphene composite material.Different Graphene contents
The optical photograph of mesoporous HZSM-a/ graphene composite material is shown in accompanying drawing 1, and accompanying drawing 2 is shown in by SEM and TEM photo, and XRD spectra is shown in accompanying drawing
4.
Embodiment 4
Weigh 120 mg Graphenes, add 8 ml deionized waters, ultrasonic disperse uniformly, weighs 7.47 g tetrapropyl oxyammonias and adds
Enter in graphene aqueous solution, stir 30 min mix homogeneously, be designated as solution A；The inclined aluminum of 50.03 mg is sequentially added in solution A
Sour sodium and 7.5 ml tetraethyl orthosilicates stir, and are designated as B solution；First by 30 DEG C of stirring 1 h of B solution, 60 DEG C of stirring 2 h,
Then heat to 80 DEG C of stirring 6 h, be then transferred to poly- four by after this B solution ethanol and deionized water cyclic washing 2 ~ 3 times
170 DEG C of crystallization 2 d of the autoclave of fluorothene liner, that is, obtain ZSM-b/ graphene composite material.This product is through ethanol
After deionized water wash 3 ~ 5 times, 100 DEG C of vacuum drying 12 h, 600 DEG C of calcining 5 h, then with the NH of 0.2 mol/L4NO3
Solution is in 80 DEG C of exchange 6 h more scrubbed, dry, calcining obtains mesoporous HZSM-b/ graphene composite material.Different graphite
Accompanying drawing 3 is shown in by SEM the and TEM photo of the mesoporous HZSM-b/ graphene composite material of alkene content, and XRD spectra is shown in accompanying drawing 5, BET result
See accompanying drawing 8 and table 1.
Embodiment 5
Weigh 120 mg Graphenes, add 6 ml deionized waters, ultrasonic disperse uniformly, weighs 0.74 g tetrapropyl oxyammonia
It is added in graphene aqueous solution, stir 30 min mix homogeneously, be designated as solution A；Sequentially add 44.4 mg different in solution A
Aluminum tripropoxide and 1.5 ml tetraethyl orthosilicates stir, and are designated as B solution；First B solution is stirred 1 h at 30 DEG C, then heat to
90 DEG C of stirring 24 h；Then it is transferred to after this B solution ethanol and deionized water cyclic washing 2 ~ 3 times in politef
180 DEG C of crystallization 3 d of autoclave of lining, that is, obtain ZSM-a/ graphene composite material.This product is through ethanol and deionization
After water washing 3 ~ 5 times, 100 DEG C of vacuum drying 12 h, 600 DEG C of calcining 5 h, then with the NH of 0.2 mol/L4NO3Solution is 80
DEG C exchange 6 h, more scrubbed, drys, calcine obtain mesoporous HZSM-a/ graphene composite material.Different Graphene contents
The optical photograph of mesoporous HZSM-a/ graphene composite material is shown in accompanying drawing 1, and accompanying drawing 2 is shown in by SEM and TEM photo, and XRD spectra is shown in accompanying drawing
4.
Embodiment 6
Weigh 120 mg Graphenes, add 8 ml deionized waters, ultrasonic disperse uniformly, weighs 1.49 g tetrapropyl oxyammonias and adds
Enter in graphene aqueous solution, stir 30 min mix homogeneously, be designated as solution A；The inclined aluminum of 10.0 mg is sequentially added in solution A
Sour sodium and 1.50 ml tetraethyl orthosilicates stir, and are designated as B solution；First by 30 DEG C of stirring 1 h of B solution, 60 DEG C of stirring 2 h,
Then heat to 80 DEG C of stirring 6 h, be then transferred to poly- four by after this B solution ethanol and deionized water cyclic washing 2 ~ 3 times
170 DEG C of crystallization 2 d of the autoclave of fluorothene liner, that is, obtain ZSM-b/ graphene composite material.This product is through ethanol
After deionized water wash 3 ~ 5 times, 100 DEG C of vacuum drying 12 h, 600 DEG C of calcining 5 h, then with the NH of 0.2 mol/L4NO3
Solution is in 80 DEG C of exchange 6 h more scrubbed, dry, 550 DEG C of calcining 5 h obtain mesoporous HZSM-b/ Graphene composite wood
Material.Accompanying drawing 3 is shown in by SEM the and TEM photo of the mesoporous HZSM-b/ graphene composite material of different Graphene contents, and XRD spectra is shown in attached
Fig. 5, BET result is shown in accompanying drawing 8 and table 1.
The structural behaviour of the ZSM-5/ graphene composite material of table 1. different content Graphene
The elementary analysiss of the ZSM-5/ graphene composite material of table 2. different content Graphene, EDS and XPS result.
The catalytic performance of the ZSM-5/ graphene composite material of table 3. different content Graphene
.
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 joined
Than for：
Graphene：5%~40%；
Molecular sieve：60%~95%；
Gained composite has quasi- two-dimensional slice structure, and the area of monolithic layer is more than 100 microns with the ratio of thickness, molecular sieve
In graphenic surface Load Balanced, mesoporous diameter is in 2 ~ 30 nm.
2. Graphene/molecular sieve composite catalyst according to claim 1 it is characterised in that：Described Graphene is one layer
One of Graphene, two layer graphenes, three layer graphenes, multi-layer graphene or graphene oxide；Described molecular sieve is ZSM-
5th, ZSM-11, SBA-15, MCM, any one in modenite.
3. Graphene/molecular sieve composite catalyst according to claim 1 it is characterised in that：Described molecular sieve is ZSM-5
When, the color of Graphene/ZSM-5 composite catalyst is black, and the micropore size of ZSM-5 expands 0.7 ± 0.1nm to, and has
Mesoporous more than 10% aperture ratio.
4. the preparation method of the Graphene/molecular sieve composite catalyst described in a kind of any one of claim 1 ~ 3, its feature exists
In：Comprise the following steps：
First Graphene, silicon source, silicon source and surfactant are mixed, be then demultiplex out graphene-containing part, then carry out crystallization
Process, finally carry out purification and remove surfactant；
Described surfactant includes：Any one in TPAOH, n-butylamine, tetraethyl amine or tetrapropyl amine；Institute
State silicon source to include：Any one in aluminum isopropylate., sodium metaaluminate, waterglass or aluminum sulfate；Described silicon source includes：Positive silicic acid second
Any one in ester, Ludox and sodium silicate.
5. Graphene/molecular sieve composite catalyst according to claim 4 preparation method it is characterised in that：Described aluminum
Source is with Al2O3Meter, described silicon source is with SiO2Meter, source of aluminium is 1 with the mol ratio of silicon source:50~80；Described surfactant with
The mol ratio of silicon source is 7 ~ 23:1；Described Graphene is 5 ~ 40% with respect to the mass percent of silicon source silicon source sum.
6. Graphene/molecular sieve composite catalyst according to claim 5 preparation method it is characterised in that：Described aluminum
When source is aluminum isopropylate., source of aluminium is 1 with the mol ratio of silicon source:62；When source of aluminium is sodium metaaluminate, source of aluminium and silicon
The mol ratio in source is 1:78.29.
7. Graphene/molecular sieve composite catalyst according to claim 4 preparation method it is characterised in that：Described mixed
The concrete operation method of conjunction process is：
（1）Graphene aqueous solution ultrasonic disperse is opened, is added thereto to surfactant, stir, obtain mixed liquor 1；
（2）Sequentially add silicon source in mixed liquor 1, silicon source stirs, obtain mixed liquor 2.
8. Graphene/molecular sieve composite catalyst according to claim 7 preparation method it is characterised in that：Also include
Following steps：
Mixed liquor 2 is carried out successively first stage crystallization and second stage crystallization, first stage crystalline substance process turns to：80 ~ 90 DEG C
Hydrothermal treatment consists；Second stage crystallization process is：90 ~ 180 DEG C of hydrothermal treatment consists, or 300 ~ 550 DEG C under anhydrous state
High-temperature process.
9. Graphene/molecular sieve composite catalyst according to claim 4 preparation method it is characterised in that：Described table
The removing method of face activating agent template is：Washing and drying after crystallization, air calcination carries out ion after removing surfactant templates again
Exchange, then calcine removing small ion/molecule again；Wash conditions are the repeated multiple times centrifuge washing of second alcohol and water；Drying temperature is
80 ~ 120 DEG C, vacuum drying 8 ~ 12 h；Template agent removing calcining heat is 550 ~ 600 DEG C, and the time is 4 ~ 6 h；After ion exchange
Calcining heat be 500 ~ 550 DEG C, the time be 4 ~ 6 h；Ion exchange conditions are：Graphene after calcining/molecular sieve composite wood
Material and NH4NO3Exchange, in 80 ~ 100 DEG C of stirring exchanges 3 ~ 5 times, exchange 2 ~ 3 h every time；Graphene/molecular sieves compound material with
NH4NO3Mass ratio be 1:2.5~4.5.
10. Graphene/the molecular sieve composite catalyst described in a kind of any one of claim 1 ~ 3 is in the contracting of benzaldehyde and glycerol
Close reaction, the esterification of caproic acid and benzyl alcohol, the Benzylation reaction of the methylation reaction of Ketohexamethylene, toluene and benzyl chloride and
Application in the condensation reaction of benzaldehyde and 2- hydroxy acetophenone.
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