CN108862304A - It is a kind of containing organic group and with micro-nano hierarchical structure hydrophobicity hydridization Si-Al molecular sieve and preparation method thereof - Google Patents

It is a kind of containing organic group and with micro-nano hierarchical structure hydrophobicity hydridization Si-Al molecular sieve and preparation method thereof Download PDF

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CN108862304A
CN108862304A CN201810865072.0A CN201810865072A CN108862304A CN 108862304 A CN108862304 A CN 108862304A CN 201810865072 A CN201810865072 A CN 201810865072A CN 108862304 A CN108862304 A CN 108862304A
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molecular sieve
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CN108862304B (en
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阳晓宇
金成静
刘欢
安亚楠
高晨
白航
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Wuhan University of Technology WUT
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Abstract

The invention belongs to field of inorganic materials, it discloses a kind of containing organic group and with the hydrophobicity hydridization Si-Al molecular sieve of micro-nano hierarchical structure, by introducing between two silicon atoms there is the organosilan of methylene to build bridge connection to replace siloxane bridge, to improve hydrophobicity；In addition, the hydrophobicity hydridization Si-Al molecular sieve is accumulated by nano particle, micro-nano structure can further enhance hydrophobic property.The present invention is using the organosilan with methylene group as silicon source, synthesizing organic-inorganic hydridization microcrystalline zeolite molecular sieve under the conditions of alkaline condition and Template-free method, while sieving matrix addition new function for inorganic molecule, the unique micro-nano structure of product and pattern can be assigned, while methylene replaces lattice oxygen atom that molecular sieve can be made to show unique oleophylic, hydrophobic surface nature.In addition, preparation method of the present invention is simple, reaction condition is mild, new catalyst, adsorbent, the research such as automatic cleaning coating can be widely applied to.

Description

It is a kind of containing organic group and with micro-nano hierarchical structure hydrophobicity hydridization silicoaluminophosphate molecular Sieve and preparation method thereof
Technical field
The invention belongs to inorganic, organic material technical fields, and in particular to one kind is containing organic group and has micro-nano classification Hydrophobicity hydridization Si-Al molecular sieve of structure and preparation method thereof.
Background technique
Zeolite molecular sieve is to interconnect the one kind constituted with regular pore canal by sharing oxygen bridge by tetrahedron element A kind of inorganic microporous material has unique crystal structure and good ion exchangeable, catalytic, adsorptivity etc. numerous Excellent properties, thus it is widely used in detergent industry, petro chemical industry, fine chemistry industry, environmental protection and the new function of development The numerous areas such as energy material.Hybrid inorganic-organic materials, this material have the characteristic of organic material and inorganic material, and energy concurrently By the compound of material function, performance complement and optimization are realized.Molecular sieve surface hydroxyl group abundant assigns its good parent Water characteristic, and the functionalization of porous material may be implemented in the introducing of organic group and adjusts the hydrophobicity of its hole wall, realizes hydrophilic Property-hydrophobic transformation, by the application of further expansion molecular sieve.Therefore, organic group is introduced into framework of molecular sieve structure Increase the big hot research direction that its hydrophobicity has become material.Currently, organic-inorganic hybrid molecule sieves general synthesis side Method has copolycondensation method and rear grafting, preparation process complexity, the severe reaction conditions being related to；And organic group is directly grafted onto Correlative study in framework of molecular sieve structure is also rarely reported.
It is well known that two key factors of super hydrophobic material are the low surface energy and its unique micro-nano knot of material Structure, the degree of roughness and porosity of material surface can greatly enhance hydrophobic property.Compared with the particle with smooth surface, tool There are layering surface topography and the particle for defining good morphology that there is rougher surface.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, providing a kind of containing organic group and with micro- Receive the hydrophobicity hydridization Si-Al molecular sieve of hierarchical structure, preparation method is simple, reaction condition is mild, and molecular sieve surface nanometer The shape and size of particle are adjustable, prominent using the molecular sieve film compact structure of its preparation, hydrophobicity and oleophylic performance, are suitble to It promotes and applies.
For realization above scheme, the technical solution adopted by the present invention is：
It is a kind of containing organic group and with micro-nano hierarchical structure hydrophobicity hydridization Si-Al molecular sieve, it be by nano particle Hydridization Si-Al molecular sieve microcrystalline balls made of accumulation have the organosilicon containing methylene in the hydridization Si-Al molecular sieve microcrystalline balls Alkane is built bridge.
It include-Si-CH in the organosilan bridge formation containing methylene in above scheme2- Si- valence link.
In above scheme, the size of the nano particle is 25-200nm, and the diameter of hydridization Si-Al molecular sieve microcrystalline balls is 200nm-5μm。
In above scheme, the nano particle is spherical, sheet or unformed shape.
In above scheme, the organosilan containing methylene is built bridge by building bridge with the organosilan containing methylene, With silicon source
A kind of preparation method of above-mentioned hydrophobicity hydridization Si-Al molecular sieve containing organic group and with micro-nano hierarchical structure, It includes the following steps：
1) silicon source is placed in lye, is hydrolyzed under room temperature and stirring condition, obtain silicon source solution I；
2) silicon source is added in lye, stirs evenly, obtains silicon source solution II；
3) silicon source solution I is added dropwise in silicon source solution II, is uniformly mixed, obtain reaction solution III；
4) reaction solution III is subjected to low-temperature hydrothermal reaction, then is centrifuged, is washed, it is dry to get the hydrophobicity hybrid silicon Aluminum molecular screen.
In above scheme, double ethyl-silicone methane (BTESM) etc. are can be selected in the silicon source.
In above scheme, source of aluminium can be selected sodium metaaluminate, potassium metaaluminate, aluminium chloride etc., alkali source can for sodium hydroxide, Potassium hydroxide etc..
In above scheme, the molar ratio of the silicon source and silicon source is 1:(0.1~1).
In above scheme, sodium hydroxide or potassium hydroxide aqueous solution etc. is can be selected in the lye.
In above scheme, water, OH in step 1)-, silicon source mass ratio (2.5~4.5):(0.05~0.6):1.
In above scheme, water, OH in step 2)-, silicon source mass ratio be (5~21):(0.4~1.6):1.
In above scheme, the low-temperature hydrothermal reaction temperature is 90~180 DEG C, and the time is 7~12d.
In above scheme, the step 1) hydrolysis time is 6~12h.
In above scheme, stirring rate described in step 1) is 500~800r/min.
In above scheme, it is described 2) described in mixing time be 0.5~2h.
The principle of the present invention is：Under the conditions of alkaline environment and Template-free method, by control synthesis condition, molecular sieve is adjusted Silica alumina ratio, organic group is introduced into framework of molecular sieve, and designing material surface roughness, with obtain have excellent performance it is hydrophobic Material.
Compared with prior art, beneficial effects of the present invention are
1) present invention is using double ethyl-silicone methane as silicon source, and sodium metaaluminate etc. is silicon source, in alkaline condition and without template Hybrid inorganic-organic microcrystalline zeolite molecular sieve has been synthesized under the conditions of agent, and methylene is accessed between two silicon atoms and forms bridging And then replace siloxane bridge, be conducive to the hydrophobic performance for improving products therefrom；And the synthetic method that is related to is simple, reaction condition temperature Be different from traditional copolycondensation method and rear grafting；
2) present invention can greatly improve the hydrophobic property of material by introducing organic group in Si-Al molecular sieve；This Outer gained hydridization Si-Al molecular sieve has the micro-nano structure as made of shape size different nano particle accumulation, can effectively improve Surface roughness further increases the hydrophobicity and lipophilicity of resulting materials；And the shape and ruler of molecular sieve surface nano particle Very little to be easy to regulate and control, applicability is wide；
3) the hydridization Si-Al molecular sieve molecule methylene group chemical activity with higher that the present invention synthesizes, after being conducive to Chemical modification and modulation process make resulting materials have good plasticity and adjustable denaturation, and expectable optimization is other Physical and chemical performance；
4) preparation process of the present invention is simple, reaction condition is mild, does not need special process equipment, reaction condition It is easy to control, it is conducive to large-scale promotion and produces.
Detailed description of the invention
Fig. 1 is the flow diagram of hydrothermal synthesis Si-Al molecular sieve containing organic group described in embodiment 1.
Fig. 2 is the SEM figure of the gained Si-Al molecular sieve containing organic group of embodiment 1 surface hydridization microcrystalline balls, wherein (b) being micro- The enlarged drawing on brilliant surface.
Fig. 3 is the performance test analysis figure of 1 gained Si-Al molecular sieve containing organic group of embodiment, wherein (a) is infrared light Spectrogram (b) is XRD diffraction pattern, is (c) BET absorption figure, (d) is thermogravimetric analysis figure.
Fig. 4 is the SEM figure of the gained Si-Al molecular sieve containing organic group of embodiment 2 surface hydridization microcrystalline balls, wherein (b) being micro- The enlarged drawing on brilliant surface.
Fig. 5 is the performance test analysis figure of 2 gained Si-Al molecular sieve containing organic group of embodiment, wherein (a) is infrared light Spectrogram (b) is XRD diffraction pattern, is (c) BET absorption figure, (d) is thermogravimetric analysis figure.
Fig. 6 is the SEM figure of the obtained Si-Al molecular sieve containing organic group under different temperatures time conditions in embodiment 3, Wherein (a) is 150 DEG C of baking ovens-hydrothermal synthesis 7d SEM figure, (b) is its enlarged drawing；It (c) is 140 DEG C of baking ovens-hydrothermal synthesis 7d SEM figure, (d) be its enlarged drawing；(e) scheme for 140 DEG C of baking ovens-hydrothermal synthesis 9d SEM, (f) be its enlarged drawing；It (g) is 120 DEG C baking oven-hydrothermal synthesis 9d SEM figure (h) is its enlarged drawing.
Fig. 7 is the IR of the Si-Al molecular sieve containing organic group synthesized under different temperatures time conditions in embodiment 3, XRD couples Compare analysis chart.
Fig. 8 is the SEM figure of the molecular sieve of organic group obtained by comparative example, wherein (b) being the enlarged drawing of microporous surface.
Fig. 9 is the performance test analysis figure of the molecular sieve containing organic group obtained by comparative example, wherein (a) is infrared spectroscopy Figure (b) is XRD diffraction pattern, is (c) BET absorption figure, (d) is thermogravimetric analysis figure.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention Content is not limited solely to the following examples.
Embodiment 1
It is a kind of containing organic group and with micro-nano hierarchical structure hydrophobicity hydridization Si-Al molecular sieve, synthetic route signal Figure is shown in Fig. 1, and specific preparation method includes the following steps：
1) 3.7375g H is successively weighed2O, 0.2763g NaOH, 1.0625g BTESM are placed in room in clean conical flask Warm open stirring 8h (revolving speed 700r/min), makes BTESM hydrolysis completely, obtains silicon source solution I；
2) 3.7375g H is successively weighed2O、0.2763g NaOH、0.3519g NaAlO2, it is placed in room in clean conical flask Warm open stirring 10min, stirs evenly, obtains silicon source solution II；
3) silicon source solution I is added dropwise in silicon source solution II, gained mixed solution room temperature opening is stirred into 20min, is filled Divide mixing, obtains reaction solution III；
4) by gained reaction solution III；It is packed into reaction kettle, is placed in 150 DEG C of baking ovens, hydrothermal synthesis 7d, kettle is taken, after cooling Centrifugation, is washed with deionized, 3 times repeatedly, then be dried overnight to get the hydrophobicity hydridization Si-Al molecular sieve.
The present embodiment products therefrom observes surface topography with field emission scanning electron microscope, Fig. 2 is as a result seen, from Fig. 2 As can be seen that the microcrystalline balls that molecular sieve film surface has size shape inhomogenous, crystal can be observed after amplification into stacked state, Compact structure measures its CA=142.4 °, and hydrophobicity is good.
External spectrum figure, XRD diffraction pattern, BET absorption figure and the thermogravimetric analysis figure of the present embodiment products therefrom are shown in Fig. 3 respectively, It is obtained from 3a) infrared spectroscopy map analysis, transmitance of each atomic group at different wave length in molecule is presented, in 3725cm-1Place has One apparent peak, is the result of oscillation of-Si-OH, in 2789cm-1And 2890cm-1Locate there are two peak, can be attributed to respectively- CH2The asymmetry and symmetrical stretching vibration of group, the two peaks clearly illustrate-CH2Group is inserted into inorganic framework；? 1650cm-1And 1485cm-1Place shows to remain the Si-CH for meeting hybrid organic-inorganic structure there are the first two peak2- Si key.X Ray diffraction analysis result is shown in Fig. 3 b), show that Si-Al molecular sieve containing organic group is in octahedra lattice structure, but crystallinity compared with It is weak.N2Specific surface area adsorption analysis result is shown in Fig. 3 c), Fig. 3 c) it is N2Adsorption/desorption thermoisopleth is to show near 0.9 in P/P0 Big adsorbing gradient out clearly illustrates that there are micropores in molecular structure；And measuring its micro pore volume is 0.21cm3/ g, is based on The micro pore volume of this figure experimental data estimation seems the micro pore volume for being less than conventional zeolite molecular sieve, the reason is that there are CH2Group Larger size it is mutually exclusive with oxygen bridge key.Thermal gravimetric analysis results are shown in Fig. 3 d), Fig. 3 d) react sial containing organic group point The son sieve thermal stability in air atmosphere under the high temperature conditions, from 100 to 400 DEG C, can be observed about 22.5% it is gradual heavy Amount loss shows that C element is evaporated at high temperature and takes off, this partial results and IR result of study are coincide very much, it was demonstrated that have Machine group methylene is successfully accessed.
Embodiment 2
It is a kind of containing organic group and with the hydrophobicity hydridization Si-Al molecular sieve of micro-nano hierarchical structure, preparation method includes Following steps：
1) 3.7375g H is successively weighed2O, 0.2763g NaOH, 1.0625g BTESM are placed in room in clean conical flask Warm open stirring 12h (revolving speed 700r/min), makes BTESM hydrolysis completely, obtains silicon source solution I；
2) 3.7375g H is successively weighed2O、0.2763g NaOH、0.7038g NaAlO2, it is placed in room in clean conical flask Warm open stirring 10min, stirs evenly, obtains silicon source solution II；
3) silicon source solution I is added dropwise in silicon source solution II, gained mixed solution room temperature opening is stirred into 20min, is filled Divide mixing, obtains reaction solution III；
4) by gained reaction solution III；It is packed into reaction kettle, is placed in 180 DEG C of baking ovens, hydrothermal synthesis 12d takes kettle, cooling After be centrifuged, be washed with deionized, 3 times repeatedly, then be dried overnight to get the hydrophobicity hydridization Si-Al molecular sieve.
The present embodiment products therefrom observes surface topography with field emission scanning electron microscope, is tested by surface contact angle To judge that the hydrophobicity on surface, the scanning electron microscope analysis result of products therefrom are shown in that Fig. 4, Fig. 4 show that molecular sieve surface growth has The inhomogenous hydridization microcrystalline balls of shape size are presented irregular stacked state layer by layer, measure its CA=122.5 °, i.e. contact angle phase To smaller, hydrophobicity is preferable.
External spectrum figure, XRD diffraction pattern, BET absorption figure and the thermogravimetric analysis figure of the present embodiment products therefrom are shown in Fig. 5 respectively, It is obtained from 5a) infrared spectroscopy map analysis, in 3456cm-1The vibration absorption peak of place-Si-OH, in 2679cm-1And 2812cm-1Place has two A peak, it was demonstrated that-CH2Group is successfully accessed.X-ray diffraction analysis result is shown in Fig. 5 b), show the silicoaluminophosphate molecular of synthesis The lattice structure of sieve is coincide with standard diagram.Fig. 5 c) it is N2Specific surface area adsorption analysis, N2Adsorption/desorption thermoisopleth, in P/P0 Nearby big adsorbing gradient is shown for 0.94, clearly illustrates that measuring its micro pore volume in molecular structure there are micropore is 0.08cm3/ g, micro pore volume are smaller.Thermal gravimetric analysis results are shown in Fig. 5 d), Fig. 5 d) react organic molecule sieve under the high temperature conditions Thermal stability in air atmosphere about observes that 17.5% gradual weight loss, C element contain from 100 to 350 DEG C Amount about reaches 21.3%, demonstrates again that the presence of organic group.The above result shows that working as silicon source too high levels and synthesis temperature mistake When height, crystallization time are too long, the micro pore volume of obtained Si-Al molecular sieve is smaller, and hydrophobic performance is also relatively poor.
Embodiment 3
It is a kind of containing organic group and with the hydrophobicity hydridization Si-Al molecular sieve of micro-nano hierarchical structure, preparation method includes Following steps：
1) 3.7375g H is successively weighed2O, 0.2763g NaOH, 1.0625g BTESM are placed in room in clean conical flask Warm open stirring 8h (revolving speed 700r/min, if room temperature is lower, using 25 DEG C of water-bath opening stirrings), has hydrolyzed BTESM Entirely, silicon source solution I is obtained；
2) 3.7375g H is successively weighed2O、0.2763g NaOH、0.1760g NaAlO2, it is placed in room in clean conical flask Warm open stirring 10min (if room temperature is lower, still needing to using 25 DEG C of water-bath opening stirrings)；It stirs evenly, obtains silicon source solution II；
3) silicon source solution I is added dropwise in silicon source solution II, gained mixed solution room temperature opening is stirred into 20min, is filled Divide mixing, obtains reaction solution III；
4) by gained reaction solution III；It is packed into reaction kettle, and is respectively placed in hydrothermal synthesis 7d in 150 DEG C of baking ovens, 140 DEG C of bakings Hydrothermal synthesis 7d in case, hydrothermal synthesis 9d in 140 DEG C of baking ovens, hydrothermal synthesis 9d takes respectively after the reaction was completed in 120 DEG C of baking ovens Kettle is centrifuged after cooling, is washed with deionized, 3 times repeatedly, then is dried overnight to get the hydrophobicity hydridization sial point Son sieve (respectively corresponding product (a), (c), (e), (g)).
The present embodiment products therefrom observes surface topography with field emission scanning electron microscope respectively, and is contacted by surface Angle test judges that the hydrophobicity on surface, the scanning electron microscope analysis result of products therefrom are shown in Fig. 6 respectively, from Fig. 6 (a), (c), (e), it can be seen that molecular sieve surface growth has a large amount of inhomogenous nano particles in (g), presentation surface large area covering is stacked Structure, and compact structure, Fig. 6 (b), (d), (f), (h) are respectively corresponding enlarged drawing, wherein (a), the two groups of surfaces (c) are Grain stack made of chondritic, and (e), the two groups of surfaces (g) be platelet stack made of chondritic, it can be seen that molecular sieve Surface hydridization microstructure size is different from shape, shows the change with experiment condition, the size of surface crystallites ball It is also changed correspondingly with shape.
(a), (c), (e), (g) four groups of products performance test analysis see Fig. 7, Fig. 7 a) be infrared spectroscopy comparative analysis figure, It 7b) is XRD diffraction comparative analysis figure, by comparing with standard PDF card, synthetic sample is sodalite structure.And by (a) (c), (e) when (g) and three groups of (c) (e) can find out that hydrothermal synthesis temperature is higher, crystallization time is longer respectively, microstructure size is got over Greatly, surface contact angle is also bigger, and hydrophobic performance is better, but hydrothermal synthesis temperature is usually no more than 180 DEG C, and crystallization time is generally not More than 12d.The present invention controls the shape of molecular sieve surface nano particle by adjusting hydrothermal synthesis temperature and crystallization time And size.
Comparative example
A kind of Si-Al molecular sieve, preparation method include the following steps：
1) 2.037g BTESM, 5.65g (20wt%) TPAOH the room temperature opening stirring in clean conical flask are successively weighed 8h, revolving speed 700r/min.
2) step 1) acquired solution is stirred into 20min using 50 DEG C of water-bath openings, keeps BTESM evenly dispersed in the solution；
3) step 2) acquired solution is packed into reaction kettle, is put into 90 DEG C of baking ovens, hydrothermal synthesis 12d is to get final product.
This comparative example products therefrom observes surface topography with field emission scanning electron microscope, is tested by surface contact angle To judge that the hydrophobicity on surface, the scanning electron microscope analysis result of products therefrom are shown in that Fig. 8, Fig. 8 show that molecular sieve surface growth has The inhomogenous microcrystalline balls of shape size can be seen that stacked in multi-layers is not presented in its microsphere surface nano particle by (b) enlarged drawing State, and it is dispersed in surface everywhere, its CA=90.4 ° is measured, hydrophobicity is poor, illustrates using obtained point of TPAOH and silicon source Son sieve can also form surface crystallites ball, but its nano particle form is irregular and structure does not have hydrophobicity.X-ray diffraction point Analysis result is shown in Fig. 9 b), by comparing with standard card, show that the molecular sieve of synthesis is octahedral structure.Fig. 9 c) it is N2Compare table Area adsorption analysis, N2Adsorption/desorption thermoisopleth, in P/P0Nearby big adsorbing gradient is shown for 0.95, is clearly illustrated point There are micropore in minor structure, measuring its micro pore volume is 0.12cm3/ g is less than and dredges using made from preparation method of the present invention The micro pore volume of aqueous molecular sieve.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified It moves within still in the protection scope of the invention.

Claims (10)

1. a kind of containing organic group and with the hydrophobicity hydridization Si-Al molecular sieve of micro-nano hierarchical structure, it is by nano particle heap Hydridization Si-Al molecular sieve microcrystalline balls made of product have the organosilan containing methylene in the hydridization Si-Al molecular sieve microcrystalline balls It builds bridge.
2. hydrophobicity hydridization Si-Al molecular sieve according to claim 1, which is characterized in that the organosilicon containing methylene Alkane includes-Si-CH in building bridge2- Si- valence link.
3. hydrophobicity hydridization Si-Al molecular sieve according to claim 1, which is characterized in that the size of the nano particle is 25-200nm, the diameter of hydridization Si-Al molecular sieve microcrystalline balls are 200nm-5 μm.
4. hydrophobicity hydridization Si-Al molecular sieve according to claim 1, which is characterized in that the nano particle be it is spherical, Sheet or unformed shape.
5. the preparation method of any one of Claims 1 to 4 hydrophobicity hydridization Si-Al molecular sieve, which is characterized in that including with Lower step：
1) silicon source is placed in lye, is hydrolyzed under room temperature and stirring condition, obtain silicon source solution I；
2) silicon source is added in lye, stirs evenly, obtains silicon source solution II；
3) silicon source solution I is added dropwise in silicon source solution II, is uniformly mixed, obtain reaction solution III；
4) reaction solution III is subjected to low-temperature hydrothermal reaction, then is centrifuged, is washed, it is dry to get the hydrophobicity hydridization sial point Son sieve.
6. preparation method according to claim 5, which is characterized in that the silicon source is double ethyl-silicone methane；Silicon source For sodium metaaluminate, potassium metaaluminate or aluminium chloride.
7. preparation method according to claim 5, which is characterized in that the molar ratio of the silicon source and silicon source is 1:(0.1~ 1)。
8. preparation method according to claim 5, which is characterized in that water, OH in step 1)-, silicon source mass ratio (2.5~ 4.5):(0.05~0.6):1；Water, OH in step 2)-, silicon source mass ratio be (5~21):(0.4~1.6):1.
9. preparation method according to claim 5, which is characterized in that the low-temperature hydrothermal reaction temperature is 90~180 DEG C, Time is 7~12d.
10. preparation method according to claim 5, which is characterized in that the step 1) hydrolysis time is 6~12h.
CN201810865072.0A 2018-08-01 2018-08-01 Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof Active CN108862304B (en)

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