CN105921176B - High sulfhydryl content mesoporous material and preparation method thereof and bifunctional catalyst and preparation method thereof - Google Patents
High sulfhydryl content mesoporous material and preparation method thereof and bifunctional catalyst and preparation method thereof Download PDFInfo
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- CN105921176B CN105921176B CN201610331291.1A CN201610331291A CN105921176B CN 105921176 B CN105921176 B CN 105921176B CN 201610331291 A CN201610331291 A CN 201610331291A CN 105921176 B CN105921176 B CN 105921176B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The method comprises the steps of firstly, preparing performed polymers, and the mixture of performed polymer alcoholic solution, ethyl alcohol and surfactant is formed a film, and successively carry out the reaction of the first hot polymerization and the reaction of the second hot polymerization, obtain polymer；Polymer is calcined under an inert atmosphere, obtains high sulfhydryl content mesoporous material.Embodiment the experimental results showed that, the high sulfhydryl content mesoporous material that method provided by the present application obtains have very high sulfhydryl content, sulfhydryl content be more than or equal to 1.5mmol/g.In addition, the high sulfhydryl content mesoporous material that the present invention obtains also has the preferable degree of order, orderly long duct and has excellent adsorption selectivity to heavy metal ion.The present invention also provides a kind of preparation methods of bifunctional catalyst.The experimental results showed that the Au-SH/SO that the present invention obtains3H-MPs catalyst has good catalytic activity to silane hydrolyzate.
Description
Technical field
The present invention relates to technical field of function materials more particularly to a kind of high sulfhydryl content mesoporous material and preparation method thereof
With bifunctional catalyst and preparation method thereof.
Background technique
Industrial wastewater (industrial wastewater) refers to the waste water and waste liquid generated in industrial processes, packet
Production waste water, production waste and cooling water are included, wherein containing the industrial production materials, intermediate product, the byproduct that outflow with water
And the pollutant generated in production process.In industrial wastewater more serious pollutant be heavy metal ion, these heavy metals from
Son mostlys come from the industries such as plating, weaving, intermetallic composite coating, Chemical Manufacture and storage batteries in industry.In industrial wastewater
Heavy metal ion is due to its biological non-biodegradable and toxic, even if at very low concentrations, can also cause to environment seriously
Pollution.
The mode of usually processing heavy metals in industrial wastewater ion mainly has the precipitation method, membrane separation process, ion-exchange, electricity
Solution and absorption method, wherein absorption method is a kind of efficient, simple and environmentally friendly way, is most widely used.It is inhaled to improve
Attached performance, it will usually the functional groups such as sulfydryl, amino, amide groups, carboxyl, sulfonic group, hydroxyl are modified in adsorbent surface, to mention
Removal rate and selectivity of the height to heavy metal ion.The mesoporous polymer material (SH-MPs) of high sulfhydryl content has high surface
The advantages that long-pending, macropore holds, duct is regular and thermal stability is high, show preferable absorption property.However, disclosed in the prior art
The sulfydryl amount of mesoporous polymer material containing sulfydryl is still lower, and absorption property is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of high sulfhydryl content mesoporous material and preparation method thereof and bifunctional catalysts
And preparation method thereof, to achieve the purpose that improve mesoporous material sulfhydryl content and bifunctional catalyst catalytic efficiency.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of high sulfhydryl content mesoporous material, comprising the following steps:
(1) preparation of performed polymer:
Under alkaline condition, thiohydroquinone and formaldehyde are mixed, obtains mixture solution；
Neutrality will be adjusted to after mixture solution heating；
The mixture solution of the neutrality remove water and except salt treatment, obtains performed polymer；
(2) mixture of the alcoholic solution comprising the performed polymer, ethyl alcohol and surfactant is formed a film, successively carries out first
Hot polymerization reaction and the reaction of the second hot polymerization, obtain polymer, and the surfactant is polyethylene oxide-polypropylene oxide-polycyclic
Oxidative ethane；
The polymer is calcined under an inert atmosphere, obtains high sulfhydryl content mesoporous material.
Preferably, it is 9.5~10.5 that the alkaline condition in the step (1), which is pH value,；
The mass ratio of the thiohydroquinone and formaldehyde is (4~6): (2.5~3.5).
Preferably, the temperature heated in the step (1) is 340~350K；
The time of the heating is 1~3 hour.
Preferably, the mass concentration of the performed polymer alcoholic solution is 15~25%；
The mass ratio of the performed polymer, ethyl alcohol and surfactant is (0.6~1.5): (8~12): (0.5~1.5).
Preferably, the temperature of the first hot polymerization reaction is 310~320K；
The time of the first hot polymerization reaction is 20~28 hours；
The temperature of the second hot polymerization reaction is 370~380K；
The time of the second hot polymerization reaction is 20~28 hours.
Preferably, the calcining is protected under the second calcination temperature successively to keep the temperature 1~3 hour under the first calcination temperature
Temperature 5~10 hours；
First calcination temperature is 350~400K；
Second calcination temperature is 600~650K.
The present invention provides the high sulfhydryl content mesoporous material that above-mentioned preparation method obtains, sulfhydryl content is more than or equal to
1.5mmol/g。
The present invention also provides a kind of preparation methods of bifunctional catalyst, comprising the following steps:
High sulfhydryl content mesoporous material is prepared according to claim 1~6 any one the method；
The high sulfhydryl content mesoporous material and gold chloride are subjected to redox reaction under solution system, obtain double function
It can catalyst；
The gold chloride is the solution of gold chloride；
The substance withdrawl syndrome of the chlorauric acid solution is 7~10mmol/L；
The ratio between amount of substance of Au in S and gold chloride in the high sulfhydryl content mesoporous material is (1~3): 1.
Preferably, the temperature of the redox reaction is -5~0 DEG C；
The time of the redox reaction is 20~30 hours.
The present invention also provides a kind of bifunctional catalyst that above-mentioned preparation method obtains, which is Au-SH/
SO3H-MPs is higher than 99% to the catalytic rate of silane hydrolyzate.
The present invention provides a kind of preparation method of high sulfhydryl content mesoporous material, the present invention is by thiohydroquinone and first
Aldehyde obtains performed polymer by certain processing under alkaline condition；By heating, calcining after the performed polymer and surfactant film forming
Obtain the mesoporous material of high sulfhydryl content.This method directly uses the phenol in thiohydroquinone substituted phenolic resin, makes material
In S content greatly increase, obtained mesoporous material have very high sulfhydryl content.Embodiment the experimental results showed that, this hair
The sulfhydryl content of the bright mesoporous material being prepared is more than or equal to 1.5mmol/g.In addition, the experimental result of embodiment is also shown that
The high sulfhydryl content mesoporous material that method provided by the invention obtains has a stronger diffraction maximum at 2 θ=0.5 °~1.0 °,
There is a weaker diffraction maximum in 2 θ=1.0 °~2.0 °, shows that material has the preferable degree of order；To Pb2+There is preferable selection
Property absorption, and removal rate is very high, and to the Ni metal beneficial to body2+、Zn2+、Cr3+Absorption property it is poor, show material have
There is excellent adsorption selectivity.
The present invention also provides a kind of preparation methods of bifunctional catalyst, will include the high sulfhydryl content mesoporous material
Redox reaction is carried out with the mixed liquor of gold chloride, obtains bifunctional catalyst.Embodiment the experimental results showed that, Au-SH/
SO3The yield that H-MPs catalyst is catalyzed silane hydrolyzate at room temperature is up to 99%, has good catalytic activity to silane hydrolyzate.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern for the SH-MPs that the embodiment of the present invention 1 obtains；
The TEM figure that Fig. 2 is the SH-MPs that the embodiment of the present invention 1 obtains；
Fig. 3 is the N for the SH-MPs that the embodiment of the present invention 1 obtains2Inhale de--attached thermoisopleth and graph of pore diameter distribution；
Fig. 4 is absorption figure of the obtained SH-MPs of the embodiment of the present invention 1 to heavy metal ion；
Fig. 5 is that the SH-MPs that the embodiment of the present invention 1 obtains and activated carbon adsorption performance compare figure.
Specific embodiment
The present invention provides a kind of preparation methods of high sulfhydryl content mesoporous material, comprising the following steps:
(1) preparation of performed polymer:
Under alkaline condition, thiohydroquinone and formaldehyde are mixed, obtains mixture solution；
Neutrality will be adjusted to after mixture solution heating；
The mixture solution of the neutrality remove water and except salt treatment, obtains performed polymer；
(2) mixture of the alcoholic solution comprising the performed polymer, ethyl alcohol and surfactant is formed a film, successively carries out first
Hot polymerization reaction and the reaction of the second hot polymerization, obtain polymer, and the surfactant is polyethylene oxide-polypropylene oxide-polycyclic
Oxidative ethane；
The polymer is calcined under an inert atmosphere, obtains high sulfhydryl content mesoporous material.
The present invention under alkaline condition, thiohydroquinone and formaldehyde is mixed, mixture solution is obtained.In the present invention
In, the alkaline condition be preferably pH value be 9.5~10.5 condition, more preferably 9.8~10.2, most preferably 10.
In the present invention, under the alkaline condition, thiohydroquinone and formaldehyde are mixed preferred specifically:
Thiohydroquinone and first part's alkaline compound solution are mixed, the first mixture is obtained；
First mixture and second part alkaline compound solution are mixed, adjusting pH value is 9.5~10.5, is obtained
Second mixture；
Second mixture and formaldehyde are mixed, mixture solution is obtained.
The present invention mixes thiohydroquinone and first part's alkaline compound solution, obtains the first mixture.This hair
The bright source to the thiohydroquinone does not have particular/special requirement, specifically can be the commercial product of thiohydroquinone.This
Invention preferably melts the thiohydroquinone, by the para hydroxybenzene phenol of the melting and first part's alkaline compound solution
Mixing, obtains the first mixture.In the present invention, the temperature of the melting is preferably 315~325K, more preferably 318~
323K, most preferably 319~321K；The time of the melting is preferably 0.4~1 hour, specifically can be 0.4 hour, 0.5
Hour, 0.6 hour, 0.8 hour or 1 hour.The present invention does not have particular/special requirement to the specific embodiment of the melting heating, has
Body can be heating water bath or oil bath heating.
In the present invention, first part's alkaline compound solution is preferably added drop-wise to thiohydroquinone by the mixing
In.The present invention does not have particular/special requirement to the rate of the dropwise addition, can be added dropwise with arbitrary rate.
In the present invention, the alkali compounds is preferably hydroxide, more preferably sodium hydroxide or potassium hydroxide.?
In the present invention, the mass concentration of first part's alkaline compound solution is preferably 15~25%, and more preferably 17~23%,
Most preferably 19~21%.In the present invention, the solvent in first part's alkaline compound solution is preferably water.
In the present invention, the mass ratio of the thiohydroquinone and first part's alkaline compound solution be preferably (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 obtained mixture.Directly drip
Obtained mixture is stirred after alkaline compound solution, so that the mixing of the first mixture is more uniform.In the present invention,
The time of first stirring is preferably 10~20 minutes, more preferably 12~18 minutes, most preferably 14~16 minutes.This hair
The bright concrete mode to the stirring does not have particular/special requirement, using the agitating mode of mixture well-known to those skilled in the art
It is stirred.
After obtaining first mixture, the present invention mixes the first mixture and second part alkaline compound solution
It closes, adjusting pH value is 9.5~10.5, obtains the second mixture.Preferably second part alkaline compound solution is added dropwise by the present invention
To the first mixture.The present invention does not have particular/special requirement to the rate of the dropwise addition, can be added dropwise with arbitrary rate.
In the present invention, the mass concentration of the second part alkaline compound solution is preferably 15~25%, more preferably
It is 17~23%, most preferably 19~21%.In the present invention, the solvent in the second part alkaline compound solution is preferred
For water.
In the present invention, the mass ratio of the thiohydroquinone and second part alkaline compound solution be preferably (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 obtained mixture, so that second is mixed
Close the more uniform of object mixing.In the present invention, the time of second stirring is preferably 5~15 minutes, more preferably 7~13
Minute, most preferably 9~11 minutes.The present invention does not have particular/special requirement to the concrete mode of the stirring, using art technology
The agitating mode of mixture known to personnel is stirred.
After obtaining second mixture, the present invention mixes the second mixture and formaldehyde, obtains mixture solution.This
Invention is preferably mixed formaldehyde in the form of formalin with second mixture.In the present invention, the formalin
Mass concentration is preferably 35~40%, specifically can be 35%, 36%, 37%, 38% or 39%.In the present invention, described
Solvent in formalin is preferably water.
In the present invention, the mass ratio of the thiohydroquinone and formaldehyde is preferably (4~6): (2.5~3.5), more excellent
It is selected as (4.5~5.5): (2.8~3.2), most preferably (5~5.4): (2.9~3.1).
After obtaining the mixture solution, the present invention is adjusted to neutrality after heating mixture solution.In the present invention, institute
The temperature for stating heating is preferably 340~350K, more preferably 342~348K, most preferably 344~346K；The heating when
Between preferably 1~3 hour, specifically can be 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours.
The present invention preferably carries out the process of the heating under agitation.The present invention does not have the concrete mode of the stirring
There is particular/special requirement, is stirred using the agitating mode of mixture well-known to those skilled in the art.
The present invention preferably cools down after the heat treatment, is more preferably cooled to room temperature.The present invention is to the drop
The mode of temperature does not have particular/special requirement, specifically can be cooling for room temperature.
The present invention does not have particular/special requirement to substance used in pH value is adjusted, specifically can be with using acidic materials
Molar concentration for hydrochloric acid solution, the more specific 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 to the mixture solution of the neutrality and removes water and salt treatment, obtains performed polymer.?
In the present invention, the water removal is preferably evaporated operation at the vaporization temperature.In the present invention, the temperature of the evaporation is preferred
For 320~330K, more preferably 322~328K, most preferably 324~326K.The present invention is to the time of the evaporation without spy
It is different to require, the mixture solution of the neutrality is preferably evaporated to constant weight.
After obtaining performed polymer, the performed polymer is preferably configured to performed polymer alcoholic solution by the present invention.In the present invention, institute
Stating the solvent in performed polymer alcoholic solution can be methanol, ethyl alcohol or propyl alcohol, and the mass concentration of the performed polymer alcoholic solution is preferably
15~25%, more preferably 17~23%, most preferably 19~21%.
The present invention forms a film the mixture of the alcoholic solution comprising the performed polymer, ethyl alcohol and surfactant, successively carries out
The reaction of first hot polymerization and the reaction of the second hot polymerization, obtain polymer, and the surfactant is polyethylene oxide-polypropylene oxide-
Polyethylene oxide.
In the present invention, the mass ratio of the performed polymer, ethyl alcohol 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 present invention
There is no particular/special requirement to the order by merging of the performed polymer alcoholic solution, ethyl alcohol and surfactant, it can be in any order
It is mixed.
In the present invention, the surfactant is polyethylene oxide-polypropylene oxide-polyethylene oxide (F127).Institute
Stating polyethylene oxide-polypropylene oxide-polyethylene oxide weight average molecular weight is preferably 12000~13000, more preferably
12300~12800, most preferably 12500~12600.
The present invention is preferably stirred the mixture of the performed polymer alcoholic solution, ethyl alcohol and surfactant.The present invention
There is no particular/special requirement to the concrete mode of the stirring, using mixture well-known to those skilled in the art agitating mode into
Row stirring.In the present invention, the time of the stirring is preferably 10~20 minutes, more preferably 12~18 minutes, optimal
It is selected as 14~16 minutes.
The present invention does not have particular/special requirement to the embodiment of the film forming, using this field have known to technical staff at
Film mode carries out, and specifically can be casting film-forming.In the present invention, the film forming carries out preferably in culture dish.?
In the present invention, the thickness of the film forming is preferably 0.1~5cm, more preferably 0.3~3cm, most preferably 0.5~1cm.
In the present invention, the temperature of the first hot polymerization reaction is preferably 310~320K, more preferably 312~318K, most
Preferably 314~316K；The time of the first hot polymerization reaction is preferably 20~28 hours, and more preferably 22~26 hours, most
Preferably 23~25 hours.In the present invention, the temperature of the second hot polymerization reaction is preferably 370~380K, and more preferably 372
~378K, most preferably 374~376K；The time of the second hot polymerization reaction is 20~28 hours, and more preferably 22~26 is small
When, most preferably 23~25 hours.
The present invention is preferably scraped with blade after obtaining the polymer, is more preferably carried out to the polymer scraped
Grinding.The present invention is not particularly limited the specific embodiment of the grinding, is ground using well-known to those skilled in the art
Mill mode is ground.
After obtaining the polymer, the present invention calcines the polymer under an inert atmosphere, obtains high sulfydryl
Content mesoporous material (SH-MPs).In the present invention, the inert atmosphere is preferably argon gas.
In the present invention, the calcining preferably successively keeps the temperature 1~3 hour under the first calcination temperature, in the second calcining
At a temperature of keep the temperature 5~10 hours.In an embodiment of the present invention, the soaking time under first calcining is 1 hour, 2 hours
Or 3 hours；Soaking time under second calcining is 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.
In the present invention, first calcination temperature is preferably 350~400K, more preferably 360~390K, most preferably
370~380K；Second calcination temperature is preferably 600~650K, more preferably 610~640K, most preferably 620~
630K。
The present invention preferably rises to the first calcination temperature from room temperature with the first heating rate, is forged with the second heating rate from first
It burns temperature and rises to the second calcination temperature.In the present invention, the first heating rate is preferably 1~3 DEG C/min, specifically can be with
For 1 DEG C/min, 2 DEG C/min or 3 DEG C/min；Second heating rate is preferably 1~3 DEG C/min, specifically can for 1 DEG C/
Min, 2 DEG C/min or 3 DEG C/min.
It is described the present invention also provides the high sulfhydryl content mesoporous material (SH-MPs) that above-mentioned preparation method is prepared
SH-MPs sulfhydryl content be more than or equal to 1.5mmol/g, have a stronger diffraction maximum at 2 θ=0.5 °~1.0 °, 2 θ=
1.0 °~2.0 ° have a weaker diffraction maximum, with the preferable degree of order and orderly long duct；To Pb2+There is preferable selection
Property absorption, removal rate is 95% or more, and to the Ni metal beneficial to body2+、Zn2+、Cr3+Absorption property it is poor.
The present invention also provides a kind of preparation methods of bifunctional catalyst, comprising the following steps:
According to the preparation method of high sulfhydryl content mesoporous material described in above-mentioned technical proposal, high sulfhydryl content is prepared and is situated between
Porous materials；
It will include the mixed liquor progress redox reaction of the high sulfhydryl content mesoporous material and gold chloride, obtain double function
It can catalyst.
In the present invention, the gold chloride is preferably chlorauric acid solution, the solvent in the chlorauric acid solution be preferably water,
Methanol, ethyl alcohol or propyl alcohol.In the present invention, the substance withdrawl syndrome of the chlorauric acid solution is preferably 7~10mmol/L, specifically
Can be 7mmol/L, 8mmol/L, 9mmol/L or 10mmol/L.
In the present invention, the molar ratio of the Au in the S and gold chloride in the high sulfhydryl content mesoporous material is preferably (1
~3): 1, it specifically can be 1:1,1.5:1,2:1,2.5:1 or 3:1.
In the present invention, the temperature of the redox reaction is preferably -5~0 DEG C, specifically can be -5 DEG C, -4
DEG C, -3 DEG C, -2 DEG C, -1 or 0 DEG C；The time of the redox reaction is preferably 20~30 hours, and more preferably 22~28 is small
When, most preferably 24~26 hours.In the present invention, the redox reaction carries out preferably in recirculation cooler.
The present invention preferably filters the product of the redox reaction, obtains bifunctional catalyst.The present invention couple
The specific embodiment of the suction filtration does not have particular/special requirement, is using suction filtration well-known to those skilled in the art operation
It can.
After the suction filtration, the present invention is preferably washed with the solid that water and/or ethyl alcohol obtain suction filtration.The present invention couple
The specific embodiment of the washing does not have particular/special requirement, is using washing operation well-known to those skilled in the art
It can.
After the washing, the present invention is preferably dried the solid after the washing, obtains difunctional urge
Agent (Au-SH/SO3H-MPs-H).In the present invention, the temperature of the drying is preferably 70~90 DEG C, more preferably 75~85
DEG C, most preferably 78~82 DEG C.In the present invention, the time of the drying is preferably 20~28 hours, more preferably 22~26
Hour, most preferably 23~25 hours.In the present invention, the drying carries out preferably in drying box.
The present invention also provides the bifunctional catalyst (Au-SH/SO that above-mentioned preparation method is prepared3H-MPs), described
Au-SH/SO3The yield that H-MPs is catalyzed silane hydrolyzate at room temperature is up to 99%, has good catalytic activity to silane hydrolyzate.
The present invention provides a kind of preparation method of high sulfhydryl content mesoporous material, the present invention is by thiohydroquinone and first
Aldehyde obtains performed polymer by certain processing under alkaline condition；By heating, calcining after the performed polymer and surfactant film forming
Obtain the mesoporous material of high sulfhydryl content.The mesoporous material that this method obtains has very high sulfhydryl content.The experiment of embodiment
The result shows that the sulfhydryl content for the mesoporous material that the present invention is prepared is more than or equal to 1.5mmol/g.In addition, the reality of embodiment
Test the high sulfhydryl content mesoporous material that result is also shown that method provided by the invention obtains has one at 2 θ=0.5 °~1.0 °
Stronger diffraction maximum has a weaker diffraction maximum in 2 θ=1.0 °~2.0 °, shows that material has the preferable degree of order；It is right
Pb2+There is preferable selective absorption, and removal rate is very high, and to the Ni metal beneficial to body2+、Zn2+、Cr3+Absorption property
It is poor, show that material has excellent adsorption selectivity.
The present invention also provides a kind of preparation methods of bifunctional catalyst, will include the high sulfhydryl content mesoporous material
Redox reaction is carried out with the mixed liquor of gold chloride, obtains bifunctional catalyst.Embodiment the experimental results showed that, Au-SH/
SO3The yield that H-MPs catalyst is catalyzed silane hydrolyzate at room temperature is up to 99%, has good catalytic activity to silane hydrolyzate.
Below with reference to embodiment to the preparation of high sulfhydryl content mesoporous material provided by the invention and bifunctional catalyst
Preparation is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The thiohydroquinone of 5.4g is weighed in dry three-necked bottle, is placed in 45 DEG C of oil bath pan and heats 0.5h extremely
Fusing.Then the configured good 20wt% sodium hydrate aqueous solution of 0.085g is slowly added dropwise, after stirring 15min, then 0.45g is added dropwise
Sodium hydrate aqueous solution.Adjusting pH value is 10, continues after stirring 10min, adds 8.1g 37wt% formalin, adjusts
It saves temperature and is cooled to room temperature after stirring 2h to 343.15K.Being adjusted to pH value with 2.0M aqueous hydrochloric acid solution is 7, is then revolved in 323K
Turn evaporation water removal, is made into the SH-MPs performed polymer ethanol solution that mass ratio is 20wt% after removing sodium chloride.
At 313K, the SH-MPs performed polymer ethanol solution, 10g ethyl alcohol and the 0.847g that are 20wt% by 5.0g mass concentration
F127 is uniformly mixed, and is layered in culture dish after stirring 15min.After keeping reaction for 24 hours at 313K, 373K respectively, scraped with blade
Polymer in lower culture dish, is calcined under tube furnace argon atmosphere after grinding, removes surfactant F127, obtained brown
Powder SH-MPs.The tube furnace leads to half an hour argon gas at room temperature first, then rises to 100 DEG C simultaneously with the rate of 2 DEG C/min
After keeping 1h, then 2 DEG C/min is warming up to 350 DEG C, keeps 7h.
The present invention detects the SH-MPs that the present embodiment obtains, and testing result is as shown in Fig. 1~3 and table 1.Its
In, Fig. 1 is the XRD diffraction pattern for the SH-MPs that the embodiment of the present invention 1 obtains, and Fig. 2 is the SH-MPs's that the embodiment of the present invention 1 obtains
TEM figure, Fig. 3 are the N for the SH-MPs that the embodiment of the present invention 1 obtains2Inhale de--attached thermoisopleth and graph of pore diameter distribution.
As shown in Figure 1, the SH-MPs that the present embodiment obtains has a stronger diffraction maximum at 2 θ=0.5 °~1.0 °,
There are a weaker diffraction maximum in 2 θ=1.0 °~2.0 °, show that sample has the preferable degree of order.A and b in Fig. 2 are respectively
[001] crystal face and [110] crystal face of SH-MPs material, as shown in Figure 2, the SH-MPs that the present embodiment obtains has orderly long hole
Road, the indirect proof presence of the meso-hole structure of material.From the figure 3, it may be seen that the SH-MPs that the present embodiment obtains belongs to Section IV type
Adsorption and desorption isotherms, and there is H1Type lags winding, further proves the presence of meso-hole structure.Table 1 is what the present embodiment obtained
The structural parameters and sulfur content data of SH-MPs.
The structural parameters and sulfur content data of SH-MPs in 1 embodiment 1 of table
In order to measure SH-MPs that the present embodiment obtains to the absorption property of heavy metal ion, the present embodiment is also inhaled
Adhesion test, the experiment be SH-MPs dosage be 20mg, liquor capacity 10ml, pH value 5.0, adsorption temp be 25 DEG C,
Oscillation rate is to adsorb the Pb of 20ppm respectively under the adsorption conditions of 150r/min2+、Fe2+、Cu2+、Zn2+And Cr3+Five kinds of huge sum of moneys
Belong to ion, adsorption test result is as shown in Figure 4.Fig. 4 is absorption of the obtained SH-MPs of the embodiment of the present invention 1 to heavy metal ion
Figure.As shown in Figure 4, the SH-MPs that the present embodiment obtains is to Pb2+There is preferable selective absorption, and removal rate is very high；And to right
The beneficial Ni metal of body2+、Zn2+、Cr3+Absorption property it is poor.
The absorption property of SH-MPs and active carbon that the present invention also obtains the present embodiment compare, and comparison result is such as
Shown in Fig. 5.Fig. 5 is that the SH-MPs that the embodiment of the present invention 1 obtains and activated carbon adsorption performance compare figure.As shown in Figure 5, this implementation
The SH-MPs that example obtains is to Pb2+Removal rate 95% or more, and active carbon is to Pb2+Removal rate be 70%.The present embodiment obtains
To the absorption property of SH-MPs to be far superior to the adsorptivity of active carbon.
Embodiment 2
The thiohydroquinone of 5.2g is weighed in dry three-necked bottle, is placed in 45 DEG C of oil bath pan and heats 0.5h extremely
Fusing.Then the configured good 20wt% sodium hydrate aqueous solution of 0.095g is slowly added dropwise, after stirring 15min, then 0.55g is added dropwise
Sodium hydrate aqueous solution.Adjusting pH value is 10, continues after stirring 10min, adds 8.5g 37wt% formalin, adjusts
It saves temperature and is cooled to room temperature after stirring 2h to 343.15K.Being adjusted to pH value with 2.0M aqueous hydrochloric acid solution is 7, is then revolved in 323K
Turn evaporation water removal, is made into the SH-MPs performed polymer ethanol solution that mass ratio is 20wt% after removing sodium chloride.
At 313K, by 5.5g mass concentration be the SH-MPs performed polymer ethanol solution of 20wt%, 10.5g ethyl alcohol and
0.847g F127 is uniformly mixed, and is layered in culture dish after stirring 15min.After keeping reaction for 24 hours at 313K, 373K respectively, use
Blade scrapes the polymer in culture dish, calcines under tube furnace argon atmosphere after grinding, removes surfactant F127, obtains
Brown powder SH-MPs.The tube furnace leads to half an hour argon gas at room temperature first, is then risen to the rate of 2 DEG C/min
100 DEG C and after keeping 1h, then 2 DEG C/min is warming up to 350 DEG C, keeps 7h.
The present invention detects the product that the present embodiment obtains according to detection method described in embodiment 1, detection knot
Fruit is consistent with embodiment 1, is no longer repeated herein.
Embodiment 3
SH-MPs the and 8.0mmol/L gold chloride ethanol solution that embodiment 1 obtains is placed in flask, so that S:Au's rubs
You are than being 1.5:1.0.Flask is placed in recirculation cooler, and adjusting temperature is 0 DEG C.It is molten by what is stirred to get after stirring for 24 hours
Liquid is filtered, and after sufficiently being washed with water and ethyl alcohol, be placed in 80 DEG C of drying boxes it is dry for 24 hours, so that Au-SH/SO be made3H-
The difunctional bifunctional catalyst of MPs.Table 2 is the Au-SH/SO that the present embodiment obtains3The structural parameters and gold content number of H-MPs
According to.
2 Au-SH/SO of table3The structural parameters and sulfur content data of H-MPs
The Au-SH/SO that the present invention also obtains the present embodiment3H-MPs and Au/SiO2, Au/HAP be catalyzed silane hydrolysis reaction
In catalytic activity compare, comparison result is as shown in table 3.
3 Au-SH/SO of table3H-MPs and Au/SiO2, Au/HAP catalytic activity compares
As shown in Table 2, when gold nanoparticle load on silica supports or is supported in hydrotalcite supports or to receive
When metre hole gold is as catalyst, such as to reach and Au-SH/SO3The identical yield of H-MPs catalyst needs to react by extending
Time, the temperature reacted that feeds intake or improves that increases catalyst realizes.Therefore Au-SH/SO3H-MPs catalyst is to silane
Hydrolysis has good catalytic activity.
Embodiment 4
SH-MPs the and 8.5mmol/L gold chloride ethanol solution that embodiment 2 obtains is placed in flask, so that S:Au's rubs
You are than being 1.8:1.0.Flask is placed in recirculation cooler, and adjusting temperature is 0 DEG C.It is molten by what is stirred to get after stirring for 24 hours
Liquid is filtered, and after sufficiently being washed with water and ethyl alcohol, be placed in 80 DEG C of drying boxes it is dry for 24 hours, so that Au-SH/SO be made3H-
MPs bifunctional catalyst.
The present invention detects the product that the present embodiment obtains according to detection method as described in example 2, detection knot
Fruit is consistent with embodiment 1, is no longer repeated herein.
As seen from the above embodiment, the high sulfhydryl content mesoporous material that the present invention obtains has very high sulfhydryl content, real
Apply example the experimental results showed that, sulfhydryl content 1.5mmol/g；The high sulfhydryl content mesoporous material that the present invention obtains also have compared with
The good degree of order, orderly long duct and there is excellent adsorption selectivity to heavy metal ion.In addition, the experiment of embodiment
As a result it is also shown that Au-SH/SO3H-MPs catalyst has good catalytic activity to silane hydrolyzate.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of high sulfhydryl content mesoporous material, comprising the following steps:
(1) preparation of performed polymer:
Under alkaline condition, thiohydroquinone and formaldehyde are mixed, obtains mixture solution；
Neutrality will be adjusted to after mixture solution heating；
The mixture solution of the neutrality remove water and except salt treatment, obtains performed polymer；
(2) mixture of the alcoholic solution comprising the performed polymer, ethyl alcohol and surfactant is formed a film, successively carries out the first hot polymerization
Reaction and the reaction of the second hot polymerization, obtain polymer, and the surfactant is polyethylene oxide-polypropylene oxide-polycyclic oxygen second
Alkane；
The polymer is calcined under an inert atmosphere, obtains high sulfhydryl content mesoporous material；
The calcining keeps the temperature 5~10 hours under the second calcination temperature successively to keep the temperature 1~3 hour under the first calcination temperature；
First calcination temperature is 350~400K；
Second calcination temperature is 600~650K.
2. preparation method according to claim 1, which is characterized in that the alkaline condition in the step (1) is that pH value is
9.5~10.5；
The mass ratio of the thiohydroquinone and formaldehyde is (4~6): (2.5~3.5).
3. preparation method according to claim 1, which is characterized in that the temperature heated in the step (1) is 340~
350K；
The time of the heating is 1~3 hour.
4. preparation method according to claim 1, which is characterized in that the mass concentration of the performed polymer alcoholic solution be 15~
25%；
The mass ratio of the performed polymer, ethyl alcohol and surfactant is (0.6~1.5): (8~12): (0.5~1.5).
5. preparation method according to claim 1, which is characterized in that the temperature of first hot polymerization reaction is 310~
320K；
The time of the first hot polymerization reaction is 20~28 hours；
The temperature of the second hot polymerization reaction is 370~380K；
The time of the second hot polymerization reaction is 20~28 hours.
6. the high sulfhydryl content mesoporous material that preparation method described in Claims 1 to 5 any one obtains, sulfhydryl content are big
In equal to 1.5mmol/g.
7. a kind of preparation method of bifunctional catalyst, comprising the following steps:
High sulfhydryl content mesoporous material is prepared according to Claims 1 to 5 any one the method；
The high sulfhydryl content mesoporous material and gold chloride are subjected to redox reaction under solution system, obtain difunctional urge
Agent；
The gold chloride is the solution of gold chloride；
The substance withdrawl syndrome of the chlorauric acid solution is 7~10mmol/L；
The ratio between amount of substance of Au in S and gold chloride in the high sulfhydryl content mesoporous material is (1~3): 1.
8. preparation method according to claim 7, which is characterized in that
The temperature of the redox reaction is -5~0 DEG C；
The time of the redox reaction is 20~30 hours.
9. the bifunctional catalyst that preparation method described in claim 7 or 8 obtains, which is Au-SH/SO3H-MPs is right
The yield of silane hydrolyzate is up to 99%.
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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 |
| CN102553529A (en) * | 2011-12-21 | 2012-07-11 | 同济大学 | Preparation method for sulfur functionalization carbon foam |
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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 |
| CN102553529A (en) * | 2011-12-21 | 2012-07-11 | 同济大学 | Preparation method for sulfur functionalization carbon foam |
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| "A Family of Highly Ordered Mesoporous Polymer Resin and Carbon Structures from Organic-Organic Self-Assembly";Yan Meng et al;《Chem. Mater.》;20060804;第18卷;第4447-4464页 * |
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