CN105921176A - High-sulfydryl-content mesoporous material, preparation method thereof, bifunctional catalyst and preparation method thereof - Google Patents
High-sulfydryl-content mesoporous material, preparation method thereof, bifunctional catalyst and preparation method thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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Abstract
The invention discloses a high-sulfydryl-content mesoporous material, a preparation method thereof, a bifunctional catalyst and a preparation method thereof. Firstly, prepolymer is prepared, the mixture of a prepolymer alcoholic solution, ethyl alcohol and a surface active agent forms a film, first heat polymerization reaction and secondary heat polymerization reaction are carried out in sequence, and polymer is obtained; the polymer is calcinated at an inert atmosphere, and a high-sulfydryl-content mesoporous material is obtained. Experiment results of embodiments show that the high-sulfydryl-content mesoporous material obtained through the method has very high sulfydryl content, the sulfydryl content is larger than or equal to 1.5 mmol/g. In addition, the obtained high-sulfydryl-content mosoporous material also has good degree of order and an ordered long pore channel and has excellent selective absorption performance for heavy metal ions. The invention further provides a preparation method of a bifunctional catalyst. Experiment results show that the obtained Au-SH/SO3H-MPs catalyst have very good catalytic activity for silane hydrolysis.
Description
Technical field
The present invention relates to technical field of function materials, particularly relate to a kind of high sulfhydryl content mesoporous material and
Preparation method and bifunctional catalyst and preparation method thereof.
Background technology
Industrial wastewater (industrial wastewater) refers to waste water and the waste liquid produced in industrial processes,
Including produce waste water, production waste and cooling water, wherein contain outflow with water commercial production materials,
The pollutant produced in intermediate product, side-product and production process.Pollution more serious in industrial wastewater
Thing is heavy metal ion, and these heavy metal ion mostly come from the plating in industry, weaving, metal add
The industries such as work, Chemical Manufacture and storage batteries.Heavy metal ion in industrial wastewater can not due to its biology
Degradability and toxic, even if at very low concentrations, also can cause serious pollution to environment.
The mode generally processing heavy metals in industrial wastewater ion mainly has the sedimentation method, membrane separation process, ion
Exchange process, electrolysis and absorption method, wherein absorption method is a kind of efficient, simple and the way of environmental protection, its
It is most widely used.In order to improve absorption property, it will usually adsorbent surface modify sulfydryl, amino,
The functional groups such as amide groups, carboxyl, sulfonic group, hydroxyl, thus improve heavy metal ion clearance and
Selectivity.The mesoporous polymer material (SH-MPs) of high sulfhydryl content has high surface, big pore volume, hole
Road is regular and heat stability advantages of higher, shows preferable absorption property.But, prior art is open
The sulfydryl amount of the mesoporous polymer material containing sulfydryl the most relatively low, absorption property is poor.
Summary of the invention
It is an object of the invention to provide a kind of high sulfhydryl content mesoporous material and preparation method thereof with difunctional
Catalyst and preparation method thereof, to reach to improve mesoporous material sulfhydryl content and bifunctional catalyst catalysis effect
The purpose of rate.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides the preparation method of a kind of high sulfhydryl content mesoporous material, comprise the following steps:
(1) preparation of performed polymer:
In the basic conditions, thiohydroquinone and formaldehyde are mixed, obtains mixture solution；
It is adjusted to neutrality after being heated by described mixture solution；
Carry out, except water and desalination process, obtaining performed polymer to the mixture solution of described neutrality；
(2) the mixture film forming of the alcoholic solution of described performed polymer, ethanol and surfactant will be comprised, depend on
Secondary first hot polymerization that carries out reacts and the reaction of the second hot polymerization, obtains polymer, and described surfactant is polycyclic
Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide)；
Described polymer is calcined under an inert atmosphere, obtains high sulfhydryl content mesoporous material.
Preferably, the alkaline condition in described step (1) be pH value be 9.5～10.5；
The mass ratio of described thiohydroquinone and formaldehyde is (4～6): (2.5～3.5).
Preferably, in described step (1), the temperature of heating is 340～350K；
The time of described heating is 1～3 hour.
Preferably, the mass concentration of described performed polymer alcoholic solution is 15～25%；
The mass ratio of described performed polymer, ethanol and surfactant is (0.6～1.5): (8～12): (0.5～1.5).
Preferably, the temperature of described first hot polymerization reaction is 310～320K；
The time of described first hot polymerization reaction is 20～28 hours；
The temperature of described second hot polymerization reaction is 370～380K；
The time of described second hot polymerization reaction is 20～28 hours.
Preferably, described calcining is to be incubated 1～3 hour under the first calcining heat successively, in the second calcining
At a temperature of be incubated 5～10 hours；
Described first calcining heat is 350～400K；
Described second calcining heat is 600～650K.
The invention provides the high sulfhydryl content mesoporous material that above-mentioned preparation method obtains, its sulfhydryl content is big
In equal to 1.5mmol/g.
Present invention also offers the preparation method of a kind of bifunctional catalyst, comprise the following steps:
High sulfhydryl content mesoporous material is prepared according to method described in claim 1～6 any one；
Described high sulfhydryl content mesoporous material and gold chloride are carried out redox reaction under solution system,
Obtain bifunctional catalyst；
Described gold chloride is the solution of gold chloride；
The substance withdrawl syndrome of described chlorauric acid solution is 7～10mmol/L；
The ratio of the amount of the material of the S in described high sulfhydryl content mesoporous material and the Au in gold chloride is
(1～3): 1.
Preferably, the temperature of described redox reaction is-5～0 DEG C；
The time of described redox reaction is 20～30 hours.
Present invention also offers the bifunctional catalyst that a kind of above-mentioned preparation method obtains, this catalyst is
Au-SH/SO3H-MPs, is higher than 99% to the catalytic rate of silane hydrolyzate.
The invention provides the preparation method of a kind of high sulfhydryl content mesoporous material, the present invention is by para hydroxybenzene
Thiophenol and formaldehyde obtain performed polymer through certain process in the basic conditions；Described performed polymer and surface are lived
Property agent film forming post-heating, calcining obtain the mesoporous material of high sulfhydryl content.The method directly uses para hydroxybenzene
Phenol in thiophenol substituted phenolic resin, makes the S content in material be greatly increased, the mesoporous material tool obtained
There is the highest sulfhydryl content.Test result indicate that of embodiment, the mesoporous material that the present invention prepares
Sulfhydryl content is more than or equal to 1.5mmol/g.Additionally, the experimental result of embodiment is it is also shown that the present invention provides
The high sulfhydryl content mesoporous material that obtains of method at 2 θ=0.5 °～1.0 °, have a stronger diffraction maximum,
2 θ=1.0 °～2.0 ° have a more weak diffraction maximum, show that material has the preferable degree of order；To Pb2+Have
Preferably selective absorption, and clearance is the highest, and to the Ni metal useful to health2+、Zn2+、Cr3+
Absorption property poor, show material have excellence adsorption selectivity.
Present invention also offers the preparation method of a kind of bifunctional catalyst, described high sulfhydryl content will be included
The mixed liquor of mesoporous material and gold chloride carries out redox reaction, obtains bifunctional catalyst.Embodiment
Test result indicate that, Au-SH/SO3H-MPs catalyst is at room temperature catalyzed the productivity of silane hydrolyzate up to
99%, silane hydrolyzate is had and is well catalyzed activity.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the SH-MPs that the embodiment of the present invention 1 obtains；
Fig. 2 is the TEM figure of the SH-MPs that the embodiment of the present invention 1 obtains；
Fig. 3 is the N of the SH-MPs that the embodiment of the present invention 1 obtains2Inhale de--attached isothermal line and graph of pore diameter distribution；
Fig. 4 is the absorption figure of the SH-MPs heavy metal ion that the embodiment of the present invention 1 obtains；
Fig. 5 is the SH-MPs that obtains of the embodiment of the present invention 1 and activated carbon adsorption performance comparison diagram.
Detailed description of the invention
The invention provides the preparation method of a kind of high sulfhydryl content mesoporous material, comprise the following steps:
(1) preparation of performed polymer:
In the basic conditions, thiohydroquinone and formaldehyde are mixed, obtains mixture solution；
It is adjusted to neutrality after being heated by described mixture solution；
Carry out, except water and desalination process, obtaining performed polymer to the mixture solution of described neutrality；
(2) the mixture film forming of the alcoholic solution of described performed polymer, ethanol and surfactant will be comprised, depend on
Secondary first hot polymerization that carries out reacts and the reaction of the second hot polymerization, obtains polymer, and described surfactant is polycyclic
Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide)；
Described polymer is calcined under an inert atmosphere, obtains high sulfhydryl content mesoporous material.
Thiohydroquinone and formaldehyde in the basic conditions, are mixed, obtain mixture solution by the present invention.
In the present invention, described alkalescence condition preferably pH value is the condition of 9.5～10.5, more preferably
9.8～10.2, most preferably 10.
In the present invention, under the conditions of described alkalescence, thiohydroquinone and formaldehyde are mixed preferably particularly as follows:
Thiohydroquinone and Part I alkaline compound solution are mixed, obtains the first mixture；
Described first mixture and Part II alkaline compound solution being mixed, regulation pH value is
9.5～10.5, obtain the second mixture；
Described second mixture and formaldehyde are mixed, obtains mixture solution.
Thiohydroquinone and Part I alkaline compound solution are mixed by the present invention, obtain the first mixing
Thing.The present invention does not has particular/special requirement to the source of described thiohydroquinone, and concrete can be to hydroxyl
The commercially available prod of phenylmercaptan..Described thiohydroquinone is preferably melted by the present invention, by described melted right
Hydroxyl phenol mixes with Part I alkaline compound solution, obtains the first mixture.In the present invention,
Described melted temperature is preferably 315～325K, more preferably 318～323K, most preferably 319～321K；
The described melted time is preferably 0.4～1 hour, concrete can be 0.4 hour, 0.5 hour, 0.6 little
Time, 0.8 hour or 1 hour.The present invention does not has particular/special requirement to the detailed description of the invention of described melted heating,
Concrete can be heating in water bath or oil bath heating.
In the present invention, described mixing is preferably and is added drop-wise to Part I alkaline compound solution to hydroxyl
In phenylmercaptan..The present invention does not has particular/special requirement to the speed of described dropping, can carry out with arbitrary speed
Dropping.
In the present invention, described alkali compounds is preferably hydroxide, more preferably sodium hydroxide or hydrogen
Potassium oxide.In the present invention, the mass concentration of described Part I alkaline compound solution is preferably
15～25%, more preferably 17～23%, most preferably 19～21%.In the present invention, described Part I
Solvent in alkaline compound solution is preferably water.
In the present invention, the mass ratio of described thiohydroquinone and Part I alkaline compound solution is excellent
Elect as (4～6): (0.001～0.1), more preferably (4.5～5.5): (0.01～0.5), most preferably
(5～5.4): (0.05～0.085).
After obtaining the first mixture, the present invention preferably carries out the first stirring to the first mixture obtained.Directly
Connect after dripping alkaline compound solution the mixture stirring obtained so that the first mixture mixing
More uniform.In the present invention, the time of described first stirring is preferably 10～20 minutes, more preferably
12～18 minutes, most preferably 14～16 minutes.The present invention does not has special wanting to the concrete mode of described stirring
Ask, use the alr mode of mixture well-known to those skilled in the art to be stirred.
After obtaining described first mixture, the present invention is by the first mixture and Part II alkali compounds
Solution mixes, and regulation pH value is 9.5～10.5, obtains the second mixture.The present invention is preferably by Part II
Alkaline compound solution is added drop-wise to the first mixture.The present invention does not has particular/special requirement to the speed of described dropping,
Can drip with arbitrary speed.
In the present invention, the mass concentration of described Part II alkaline compound solution is preferably 15～25%,
More preferably 17～23%, most preferably 19～21%.In the present invention, described Part II alkalescence chemical combination
Solvent in thing solution is preferably water.
In the present invention, the mass ratio of described thiohydroquinone and Part II alkaline compound solution is excellent
Elect as (4～6): (0.01～1), more preferably (4.5～5.5): (0.1～0.8), most preferably (5～5.4): (0.45～0.6).
After obtaining the second mixture, the present invention preferably carries out the second stirring to the second mixture obtained, and makes
Obtain the more uniform of the second mixture mixing.In the present invention, the time of described second stirring is preferably 5～15
Minute, more preferably 7～13 minutes, most preferably 9～11 minutes.The present invention is concrete to described stirring
Mode does not has particular/special requirement, uses the alr mode of mixture well-known to those skilled in the art to stir
Mix.
After obtaining described second mixture, the second mixture and formaldehyde are mixed by the present invention, are mixed
Thing solution.Formaldehyde is preferably mixed with described second mixture by the present invention with the form of formalin.At this
In invention, the mass concentration of described formalin is preferably 35～40%, concrete can be 35%, 36%,
37%, 38% or 39%.In the present invention, the solvent in described formalin is preferably water.
In the present invention, the mass ratio of described thiohydroquinone and formaldehyde is preferably (4～6): (2.5～3.5),
More preferably (4.5～5.5): (2.8～3.2), most preferably (5～5.4): (2.9～3.1).
After obtaining described mixture solution, the present invention is adjusted to neutrality after being heated by mixture solution.At this
In invention, the temperature of described heating is preferably 340～350K, more preferably 342～348K, most preferably
344～346K；The time of described heating is preferably 1～3 hour, concrete can be 1 hour, 1.5 hours,
2 hours, 2.5 hours or 3 hours.
The present invention carries out the process of described heating the most under agitation.The present invention tool to described stirring
Body mode does not has particular/special requirement, uses the alr mode of mixture well-known to those skilled in the art to carry out
Stir.
The present invention preferably lowers the temperature after described heat treated, preferred is cooled to room temperature.The present invention
The mode of described cooling is not had particular/special requirement, and concrete can be room temperature cooling.
The material that regulation pH value is used by the present invention does not has particular/special requirement, uses acidic materials, tool
Body can be hydrochloric acid solution, and the molar concentration of the most described hydrochloric acid solution is preferably 0.1～3mol/L,
More preferably 0.5～2.5mol/L, most preferably 1～2mol/L.
The present invention carries out rotary evaporation and removes water and salt treatment the mixture solution of described neutrality, obtains pre-
Aggressiveness.In the present invention, described being evaporated the most at the vaporization temperature except water operates.In the present invention
In, the temperature of described evaporation is preferably 320～330K, more preferably 322～328K, most preferably
324～326K.The present invention does not has particular/special requirement to the time of described evaporation, preferably by the mixing of described neutrality
Thing solution evaporation is to constant weight.
After obtaining performed polymer, described performed polymer is preferably configured to performed polymer alcoholic solution by the present invention.At this
In invention, the solvent in described performed polymer alcoholic solution can be methanol, ethanol or propanol, described performed polymer
The mass concentration of alcoholic solution is preferably 15～25%, more preferably 17～23%, most preferably 19～21%.
The present invention will comprise the mixture film forming of the alcoholic solution of described performed polymer, ethanol and surfactant,
Carrying out the first hot polymerization reaction and the reaction of the second hot polymerization successively, obtain polymer, described surfactant is poly-
Oxide-polypropylene oxide-poly(ethylene oxide).
In the present invention, the mass ratio of described performed polymer, ethanol and surfactant is preferably
(0.6～1.5): (8～12): (0.5～1.5), more preferably (0.8～1.3): (9～11): (0.7～1), most preferably
1:10:0.847.The order by merging of described performed polymer alcoholic solution, ethanol and surfactant is not had by the present invention
Particular/special requirement, can mix in any order.
In the present invention, described surfactant is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)
(F127).The weight average molecular weight of described poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) is preferably
12000～13000, more preferably 12300～12800, most preferably 12500～12600.
The mixture of described performed polymer alcoholic solution, ethanol and surfactant is preferably stirred by the present invention.
The present invention does not has particular/special requirement to the concrete mode of described stirring, uses well-known to those skilled in the art
The alr mode of mixture is stirred.In the present invention, the time of described stirring is preferably 10～20
Minute, more preferably 12～18 minutes, most preferably 14～16 minutes.
The present invention does not has particular/special requirement to the embodiment of described film forming, uses this area to have technical staff institute
Known to thin film-forming method carry out, concrete can be casting film-forming.In the present invention, described film forming
Preferably carry out in culture dish.In the present invention, the thickness of described film forming is preferably 0.1～5cm, more preferably
It is 0.3～3cm, most preferably 0.5～1cm.
In the present invention, the temperature of described first hot polymerization reaction is preferably 310～320K, more preferably
312～318K, most preferably 314～316K；The time of described first hot polymerization reaction is preferably 20～28 hours,
More preferably 22～26 hours, most preferably 23～25 hours.In the present invention, described second hot polymerization is anti-
The temperature answered is preferably 370～380K, more preferably 372～378K, most preferably 374～376K；Described
The time of the second hot polymerization reaction is 20～28 hours, more preferably 22～26 hours, most preferably 23～25
Hour.
The present invention preferred blade after obtaining described polymer scrapes, preferred poly-to scrape
Compound is ground.The detailed description of the invention of described grinding is not particularly limited by the present invention, uses ability
Lapping mode known to field technique personnel is ground.
After obtaining described polymer, described polymer is calcined by the present invention under an inert atmosphere,
To high sulfhydryl content mesoporous material (SH-MPs).In the present invention, described inert atmosphere is preferably argon.
In the present invention, described calcining is preferably and is incubated 1～3 hour under the first calcining heat successively,
It is incubated 5～10 hours under second calcining heat.In an embodiment of the present invention, the guarantor under described first calcining
The temperature time is 1 hour, 2 hours or 3 hours；Temperature retention time under described second calcining is 5 hours, 6
Hour, 7 hours, 8 hours, 9 hours or 10 hours.
In the present invention, described first calcining heat is preferably 350～400K, more preferably 360～390K,
Most preferably 370～380K；Described second calcining heat is preferably 600～650K, more preferably
610～640K, most preferably 620～630K.
The present invention preferably rises to the first calcining heat with the first heating rate from room temperature, with the second heating rate
The second calcining heat is risen to from the first calcining heat.In the present invention, described first heating rate is preferably
1～3 DEG C/min, that concrete can be 1 DEG C/min, 2 DEG C/min or 3 DEG C/min；Described second heating rate
Being preferably 1～3 DEG C/min, that concrete can be 1 DEG C/min, 2 DEG C/min or 3 DEG C/min.
Present invention also offers the high sulfhydryl content mesoporous material that above-mentioned preparation method prepares
(SH-MPs), described SH-MPs sulfhydryl content is more than or equal to 1.5mmol/g, 2 θ=0.5 °～1.0 °
There is a stronger diffraction maximum at place, has a more weak diffraction maximum 2 θ=1.0 °～2.0 °, has preferably
The degree of order and orderly long duct；To Pb2+Have preferable selective absorption, clearance more than 95%,
And to the Ni metal useful to health2+、Zn2+、Cr3+Absorption property poor.
Present invention also offers the preparation method of a kind of bifunctional catalyst, comprise the following steps:
According to the preparation method of sulfhydryl content mesoporous material high described in technique scheme, prepare high mercapto
Base content mesoporous material；
The mixed liquor including described high sulfhydryl content mesoporous material and gold chloride is carried out redox reaction,
Obtain bifunctional catalyst.
In the present invention, described gold chloride is preferably chlorauric acid solution, the solvent in described chlorauric acid solution
It is preferably water, methanol, ethanol or propanol.In the present invention, the amount of the material of described chlorauric acid solution is dense
Degree is preferably 7～10mmol/L, concrete can be 7mmol/L, 8mmol/L, 9mmol/L or
10mmol/L。
In the present invention, the S in described high sulfhydryl content mesoporous material and the mol ratio of the Au in gold chloride
Being preferably (1～3): 1, that concrete can be 1:1,1.5:1,2:1,2.5:1 or 3:1.
In the present invention, the temperature of described redox reaction is preferably-5～0 DEG C, concrete can be-5 DEG C,
-4 DEG C ,-3 DEG C ,-2 DEG C ,-1 or 0 DEG C；The time of described redox reaction is preferably 20～30 hours,
More preferably 22～28 hours, most preferably 24～26 hours.In the present invention, described oxidoreduction is anti-
Should preferably carry out in recirculation cooler.
The present invention preferably carries out sucking filtration to the product of described redox reaction, obtains bifunctional catalyst.
The present invention does not has particular/special requirement to the detailed description of the invention of described sucking filtration, uses those skilled in the art institute ripe
The sucking filtration operation known is carried out.
After described sucking filtration, the solid that sucking filtration is preferably obtained by the present invention with water and/or ethanol washs.
The present invention does not has particular/special requirement to the detailed description of the invention of described washing, uses those skilled in the art institute ripe
The washing operation known is carried out.
After described washing, the solid after described washing is preferably dried by the present invention, obtains difunctional
Bifunctional catalyst (Au-SH/SO3H-MPs-H).In the present invention, described dry temperature is preferably
70～90 DEG C, more preferably 75～85 DEG C, most preferably 78～82 DEG C.In the present invention, described dry
Time is preferably 20～28 hours, more preferably 22～26 hours, most preferably 23～25 hours.At this
In invention, described being dried preferably is carried out in drying baker.
Present invention also offers the bifunctional catalyst that above-mentioned preparation method prepares
(Au-SH/SO3H-MPs), described Au-SH/SO3H-MPs is at room temperature catalyzed the productivity of silane hydrolyzate up to
99%, silane hydrolyzate is had and is well catalyzed activity.
The invention provides the preparation method of a kind of high sulfhydryl content mesoporous material, the present invention is by para hydroxybenzene
Thiophenol and formaldehyde obtain performed polymer through certain process in the basic conditions；Described performed polymer and surface are lived
Property agent film forming post-heating, calcining obtain the mesoporous material of high sulfhydryl content.The mesoporous material that the method obtains
There is the highest sulfhydryl content.Test result indicate that of embodiment, the mesoporous material that the present invention prepares
Sulfhydryl content more than or equal to 1.5mmol/g.Additionally, the experimental result of embodiment is it is also shown that the present invention carries
The high sulfhydryl content mesoporous material that the method for confession obtains has a stronger diffraction maximum at 2 θ=0.5 °～1.0 °,
There is a more weak diffraction maximum 2 θ=1.0 °～2.0 °, show that material has the preferable degree of order；To Pb2+
There is preferable selective absorption, and clearance is the highest, and to the Ni metal useful to health2+、Zn2+、Cr3+
Absorption property poor, show material have excellence adsorption selectivity.
Present invention also offers the preparation method of a kind of bifunctional catalyst, described high sulfhydryl content will be included
The mixed liquor of mesoporous material and gold chloride carries out redox reaction, obtains bifunctional catalyst.Embodiment
Test result indicate that, Au-SH/SO3H-MPs catalyst is at room temperature catalyzed the productivity of silane hydrolyzate up to
99%, silane hydrolyzate is had and is well catalyzed activity.
The preparation of the high sulfhydryl content mesoporous material present invention provided below in conjunction with embodiment and difunctional urge
The preparation of agent is described in detail, but they can not be interpreted as the limit to scope
Fixed.
Embodiment 1
Weigh the thiohydroquinone of 5.4g in dry three-necked bottle, be placed in the oil bath pan of 45 DEG C adding
Hot 0.5h is to fusing.Then the configured good 20wt% sodium hydrate aqueous solution of 0.085g it is slowly added dropwise,
After stirring 15min, then drip the sodium hydrate aqueous solution of 0.45g.Regulation pH value is 10, continues to stir
After mixing 10min, add 8.1g 37wt% formalin, adjust the temperature to 343.15K, stir 2h
After, it is cooled to room temperature.Being adjusted to pH value with 2.0M aqueous hydrochloric acid solution is 7, rotates at 323K subsequently and steams
Send out except water, be made into, after removing sodium chloride, the SH-MPs performed polymer ethanol solution that mass ratio is 20wt%.
Under 313K, by SH-MPs performed polymer ethanol solution that 5.0g mass concentration is 20wt%, 10
G ethanol and 0.847g F127 uniformly mix, and are layered in culture dish after stirring 15min.Respectively at 313K,
After keeping reaction 24h under 373K, scrape the polymer in culture dish with blade, at tube furnace after grinding
Calcine under argon gas atmosphere, remove surfactant F127, brown powder SH-MPs obtained.Described pipe
Formula stove the most at room temperature leads to argon half an hour, then rises to 100 DEG C with the speed of 2 DEG C/min and keeps 1h
After, then 2 DEG C/min is warming up to 350 DEG C, keeps 7h.
The SH-MPs that the present embodiment is obtained by the present invention is detected, testing result such as Fig. 1～3 and table 1
Shown in.Wherein, Fig. 1 is the XRD diffraction pattern of the SH-MPs that the embodiment of the present invention 1 obtains, and Fig. 2 is
The TEM figure of the SH-MPs that the embodiment of the present invention 1 obtains, Fig. 3 is that the embodiment of the present invention 1 obtains
The N of SH-MPs2Inhale de--attached isothermal line and graph of pore diameter distribution.
As shown in Figure 1, the SH-MPs that the present embodiment obtains have at 2 θ=0.5 °～1.0 ° one stronger
Diffraction maximum, has a more weak diffraction maximum 2 θ=1.0 °～2.0 °, shows that sample has the preferable degree of order.
A and b in Fig. 2 is SH-MPs material [001] crystal face and [110] crystal face respectively, as shown in Figure 2,
The SH-MPs that the present embodiment obtains has orderly long duct, the meso-hole structure of indirect proof material
Exist.From the figure 3, it may be seen that the SH-MPs that the present embodiment obtains belongs to iv type Adsorption and desorption isotherms,
And there is H1The delayed winding of type, proves the existence of meso-hole structure further.Table 1 obtains for the present embodiment
The structural parameters of SH-MPs and sulfur content data.
The structural parameters of SH-MPs and sulfur content data in table 1 embodiment 1
In order to measure the absorption property of the SH-MPs heavy metal ion that the present embodiment obtains, the present embodiment
Also having carried out adsorption test, this experiment is to be 20mg at the consumption of SH-MPs, and liquor capacity is 10ml,
PH value is 5.0, and adsorption temp is 25 DEG C, and oscillation rate is under the adsorption conditions of 150r/min, inhales respectively
The Pb of attached 20ppm2+、Fe2+、Cu2+、Zn2+And Cr3+Five heavy metal species ions, adsorption test result
As shown in Figure 4.Fig. 4 is the absorption figure of the SH-MPs heavy metal ion that the embodiment of the present invention 1 obtains.
As shown in Figure 4, the SH-MPs that the present embodiment obtains is to Pb2+There is preferable selective absorption, and remove
Rate is the highest；And to the Ni metal useful to health2+、Zn2+、Cr3+Absorption property poor.
The SH-MPs that the present embodiment is also obtained by the present invention compares with the absorption property of activated carbon,
Comparative result is as shown in Figure 5.Fig. 5 is the SH-MPs that obtains of the embodiment of the present invention 1 and activated carbon adsorption
Performance comparision figure.As shown in Figure 5, the SH-MPs that the present embodiment obtains is to Pb2+Clearance 95%
Above, and activated carbon is to Pb2+Clearance be 70%.The adsorptivity of the SH-MPs that the present embodiment obtains
The adsorptivity of energy activated carbon to be far superior to.
Embodiment 2
Weigh the thiohydroquinone of 5.2g in dry three-necked bottle, be placed in the oil bath pan of 45 DEG C adding
Hot 0.5h is to fusing.Then the configured good 20wt% sodium hydrate aqueous solution of 0.095g it is slowly added dropwise,
After stirring 15min, then drip the sodium hydrate aqueous solution of 0.55g.Regulation pH value is 10, continues to stir
After mixing 10min, add 8.5g 37wt% formalin, adjust the temperature to 343.15K, stir 2h
After, it is cooled to room temperature.Being adjusted to pH value with 2.0M aqueous hydrochloric acid solution is 7, rotates at 323K subsequently and steams
Send out except water, be made into, after removing sodium chloride, the SH-MPs performed polymer ethanol solution that mass ratio is 20wt%.
Under 313K, by SH-MPs performed polymer ethanol solution that 5.5g mass concentration is 20wt%, 10.5
G ethanol and 0.847g F127 uniformly mix, and are layered in culture dish after stirring 15min.Respectively at 313K,
After keeping reaction 24h under 373K, scrape the polymer in culture dish with blade, at tube furnace after grinding
Calcine under argon gas atmosphere, remove surfactant F127, brown powder SH-MPs obtained.Described pipe
Formula stove the most at room temperature leads to argon half an hour, then rises to 100 DEG C with the speed of 2 DEG C/min and keeps 1h
After, then 2 DEG C/min is warming up to 350 DEG C, keeps 7h.
The product that the present embodiment is obtained by the present invention according to the detection method described in embodiment 1 is detected,
Testing result is consistent with embodiment 1, no longer repeats at this.
Embodiment 3
SH-MPs and 8.0mmol/L gold chloride ethanol solution embodiment 1 obtained is placed in flask,
The mol ratio making S:Au is 1.5:1.0.Flask is placed in recirculation cooler, and to regulate temperature be 0 DEG C.
After stirring 24h, solution stirring obtained carries out sucking filtration, and after fully washing with water and ethanol, is placed on
80 DEG C of drying baker are dried 24h, thus prepare Au-SH/SO3The difunctional bifunctional catalyst of H-MPs.
The Au-SH/SO that table 2 obtains for the present embodiment3The structural parameters of H-MPs and gold content data.
Table 2 Au-SH/SO3The structural parameters of H-MPs and sulfur content data
The Au-SH/SO that the present embodiment is also obtained by the present invention3H-MPs and Au/SiO2, Au/HAP catalysis
Catalysis activity in silane hydrolysis reaction compares, and comparative result is as shown in table 3.
Table 3 Au-SH/SO3H-MPs and Au/SiO2, Au/HAP be catalyzed expression activitiy
As shown in Table 2, on silica supports or it is supported on hydrotalcite supports when golden nanometer particle load
Upper or during using nano-hole golden as catalyst, as reached and Au-SH/SO3H-MPs catalyst is identical
Productivity, is needed the time reacted by prolongation, increases feeding intake or improve the temperature of reaction and coming real of catalyst
Existing.Therefore Au-SH/SO3Silane hydrolyzate is had and is well catalyzed activity by H-MPs catalyst.
Embodiment 4
SH-MPs and 8.5mmol/L gold chloride ethanol solution embodiment 2 obtained is placed in flask,
The mol ratio making S:Au is 1.8:1.0.Flask is placed in recirculation cooler, and to regulate temperature be 0 DEG C.
After stirring 24h, solution stirring obtained carries out sucking filtration, and after fully washing with water and ethanol, is placed on
80 DEG C of drying baker are dried 24h, thus prepare Au-SH/SO3H-MPs bifunctional catalyst.
The product that the present embodiment is obtained by the present invention according to the detection method described in embodiment 2 is detected,
Testing result is consistent with embodiment 1, no longer repeats at this.
As seen from the above embodiment, the high sulfhydryl content mesoporous material that the present invention obtains has the highest sulfydryl
Content, test result indicate that of embodiment, sulfhydryl content is 1.5mmol/g；The high sulfydryl that the present invention obtains
Content mesoporous material also has the preferable degree of order, orderly long duct and heavy metal ion and has excellent
Different adsorption selectivity.Additionally, the experimental result of embodiment is it is also shown that Au-SH/SO3H-MPs catalyst
Silane hydrolyzate is had and is well catalyzed activity.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit
Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a preparation method for high sulfhydryl content mesoporous material, comprises the following steps:
(1) preparation of performed polymer:
In the basic conditions, thiohydroquinone and formaldehyde are mixed, obtains mixture solution；
It is adjusted to neutrality after being heated by described mixture solution；
Carry out, except water and desalination process, obtaining performed polymer to the mixture solution of described neutrality；
(2) the mixture film forming of the alcoholic solution of described performed polymer, ethanol and surfactant will be comprised, depend on
Secondary first hot polymerization that carries out reacts and the reaction of the second hot polymerization, obtains polymer, and described surfactant is polycyclic
Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide)；
Described polymer is calcined under an inert atmosphere, obtains high sulfhydryl content mesoporous material.
Preparation method the most according to claim 1, it is characterised in that in described step (1)
Alkalescence condition be pH value be 9.5～10.5；
The mass ratio of described thiohydroquinone and formaldehyde is (4～6): (2.5～3.5).
Preparation method the most according to claim 1, it is characterised in that described step adds in (1)
The temperature of heat is 340～350K；
The time of described heating is 1～3 hour.
Preparation method the most according to claim 1, it is characterised in that described performed polymer alcoholic solution
Mass concentration is 15～25%；
The mass ratio of described performed polymer, ethanol and surfactant is (0.6～1.5): (8～12): (0.5～1.5).
Preparation method the most according to claim 1, it is characterised in that described first hot polymerization reaction
Temperature is 310～320K；
The time of described first hot polymerization reaction is 20～28 hours；
The temperature of described second hot polymerization reaction is 370～380K；
The time of described second hot polymerization reaction is 20～28 hours.
Preparation method the most according to claim 1, it is characterised in that described calcining is successively
It is incubated 1～3 hour under one calcining heat, under the second calcining heat, is incubated 5～10 hours；
Described first calcining heat is 350～400K；
Described second calcining heat is 600～650K.
7. the high sulfhydryl content mesoporous material that the preparation method described in claim 1～6 any one obtains,
Its sulfhydryl content is more than or equal to 1.5mmol/g.
8. a preparation method for bifunctional catalyst, comprises the following steps:
High sulfhydryl content mesoporous material is prepared according to method described in claim 1～6 any one；
Described high sulfhydryl content mesoporous material and gold chloride are carried out redox reaction under solution system,
Obtain bifunctional catalyst；
Described gold chloride is the solution of gold chloride；
The substance withdrawl syndrome of described chlorauric acid solution is 7～10mmol/L；
The ratio of the amount of the material of the S in described high sulfhydryl content mesoporous material and the Au in gold chloride is
(1～3): 1.
Preparation method the most according to claim 8, it is characterised in that
The temperature of described redox reaction is-5～0 DEG C；
The time of described redox reaction is 20～30 hours.
10. the bifunctional catalyst that the preparation method described in claim 8 or 9 obtains, this catalyst is
Au-SH/SO3H-MPs, is higher than 99% to the catalytic rate of silane hydrolyzate.
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| CN101745366A (en) * | 2010-01-29 | 2010-06-23 | 上海师范大学 | Mercapto-functionalized organic inorganic hybrid ordered mesoporous silicon material and preparation method thereof |
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| CN107245136A (en) * | 2017-05-13 | 2017-10-13 | 淮阴师范学院 | A kind of ordered mesoporous polymer material and its preparation method and application |
| CN107245136B (en) * | 2017-05-13 | 2019-01-25 | 淮阴师范学院 | A kind of ordered mesoporous polymer material and its preparation method and application |
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