CN104646033B - A kind of sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst and preparation method and application - Google Patents
A kind of sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst and its preparation method and application, the present invention prepares sulfonic group mesoporous silicon dioxide nano microsphere using sulfonic group Graft Method, then the sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere homogeneous with duct, specific surface area is big, heat stability is good is as carrier, by covalent bond effect, transition metal ionss are connected on the functional groups in duct, and under conditions of hydrothermal calcine, transition metal ionss growth in situ in duct for the absorption is nano-metal-oxide.Preparation method is simple of the present invention is practical, and the catalyst of preparation shows good catalysis activity in the reaction of catalytic activation hydrogen peroxide oxidation, and not only catalyst amount is few, and reaction condition is gentle, and can be recycled for multiple times, and has good commercial application potentiality.
Description
Technical field
The present invention relates to a kind of functionalization support materials for catalysts and its preparation method and application, particularly a kind of sulfonic acid work(
Metal oxide-loaded heterogeneous catalysis of mesoporous silicon dioxide micro-sphere and its preparation method and application can be changed, belong to inorganic metal
Catalysis material preparation and the technical field of catalytic applications.
Background technology
At present, catalytic oxidation of hydrogen peroxide technology has been widely used in petrochemical industry, pharmacy, environmental conservation, agricultural
In field, but develop high-performance supported type catalyst and become the key accelerating catalytic oxidation of hydrogen peroxide reaction to carry out.In recent years
Come, silicon dioxide series porous material as catalyst carrier have bigger serface, good heat, chemical stability, three
Tie up the advantages such as orderly pore passage structure and nontoxic and biocompatibility height, cause the extensive concern of scholars, in catalysis neck
Domain shows great development potentiality.Using different in patent CN103657726A, CN102701297A and CN102764617A
Structural silica dioxide material is that carrier loaded monometallic, metal-oxide etc. are applied in different catalytic reactions, all shows
Higher catalytic performance.Although earth silicon material is widely applied in theoretical research as carrier, institute at present
, often there are some problems in actual catalytic reaction process in the most of silica supports employed in the method for report
Need urgent solution：(1) on silica supports, supported active bit number of points is less, active component skewness on carrier
Even, easy reunion, thus reduce the activity of supported catalyst；(2) due between avtive spot and carrier in catalytic oxidation
Adhesion is weaker, promotes the active component loading that leakage phenomenon occurs, shortens the service life of catalyst, increased the one-tenth of operation
This.These problems all seriously limit the extensive application of silicon dioxide series material load type catalyst.
Content of the invention
It is an object of the invention to provide one kind is used for being catalyzed hydrogen peroxide (H2O2) oxidation reaction the mesoporous dioxy of sulfonic acid funtionalized
SiClx microsphere supported catalyst and preparation method thereof, solves existing nano metal cluster in mesoporous silicon oxide material using the method
On material, load capacity is low, distributional pattern is uneven and both combine not closely the problems such as, prepared catalysis material has hyperoxia
Change the Activity and stabill of reaction, expand the scope of application of reaction.
The present invention with sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere as carrier, by covalent bond effect by transition metal ionss
It is connected on the functional groups in duct, and under conditions of solvent thermal-roasting, make absorption metal ion source position life in duct
A length of nano oxidized metal cluster.
The technical solution used in the present invention is：
A kind of preparation method of sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst, methods described
Comprise the following steps：
(1) mesoporous silicon dioxide nano microsphere is prepared using anion surfactant template：By tetraethyl orthosilicate and
Co-structured directed agents are added to dissolved with the hydrochloric acid solution of anion surfactant, and 50～120 DEG C of heating (preferably 60 DEG C) is anti-
Answer 10～36h (preferably 15～18h), after the completion of reaction, centrifugation, solid washing, vacuum drying obtain SiO2Nano microsphere；SiO2
Nano microsphere, in 400～800 DEG C of (preferably 600 DEG C) temperature lower calcination 4～8h (preferably 6h), removes the surface activity in duct
Agent, prepared mesoporous silicon dioxide nano microsphere；
Described co-structured directed agents are 3- aminopropyl triethoxysilane (APES), and described anion surfactant is N-
Sodium lauroyl sarcosine or dodecylbenzene sodium sulfonate, preferably N- sodium lauroyl sarcosine；
Described tetraethyl orthosilicate, co-structured directed agents, the ratio of the amount of the material of anion surfactant are 100：4～
12：4～40, preferably 100：7～8：15～20.
The described hydrochloric acid solution dissolved with anion surfactant is anion surfactant to be dissolved in dilute hydrochloric acid join
It is obtained, in dilute hydrochloric acid, the concentration of HCl is usually 0.05～0.2mol/L (preferably 0.1mol/L), dissolved with anion surface active
In the hydrochloric acid solution of agent, the concentration of anion surfactant is usually 20～50mmol/L, preferably 30mmol/L.
(2) sulfonic group mesoporous silicon dioxide nano microsphere is prepared using sulfonic group Graft Method：By step (1) prepare mesoporous
Silicon dioxide nanosphere is immersed in dichloromethane, after ultrasonic disperse, adds chlorosulfonic acid, is reacted under ultrasonic vibration,
0.5～3h is reacted under room temperature, after the completion of reaction, centrifugation, solid washing, vacuum drying, prepared sulfonic group mesoporous silicon oxide is received
Meter Wei Qiu；
Described mesoporous silicon dioxide nano microsphere, the mass ratio of chlorosulfonic acid are 1：2～15, preferably 1：5～10, more preferably 1：
7.
Described ultrasonic condition generally power 50～200w (preferably 100W), frequency 10～70kHz (preferably 50～
60kHz).
The volumetric usage of described dichloromethane is typically calculated as 10～50mL/g with the quality of mesoporous silicon dioxide nano microsphere.
(3) micro-ball load catalyst is prepared using hydro-thermal-roasting method：Sulfonic group meso-porous titanium dioxide prepared by step (2)
Silicon Nano microsphere and water-soluble transition metal salt add in deionized water, carry out hydro-thermal reaction after stirring and evenly mixing, it is heated to 50～
Reaction 4～20h (preferably 8h) at a temperature of 150 DEG C (preferably 60 DEG C), after the completion of reaction, centrifugation, solid cleaning, vacuum drying, institute
Obtain solid product to be placed in Muffle furnace, 150～600 DEG C of (preferably 180 DEG C) temperature lower calcination 2～6h, prepare sulfonate functional
Change mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst.
Described water-soluble transition metal salt is the nitrate of transition metal and/or acetate, described transition metal is Fe, V,
A kind of or two kinds in Ni, Cu, Co, Mn.Preferably described water-soluble transition metal salt is one of copper nitrate, manganese acetate or two
Kind, the catalyst preparing is CuO/ sulfonic acid funtionalized SiO2Microsphere, MnO2/ sulfonic acid funtionalized SiO2Microsphere or Cu2- xMn0.5xO2/ sulfonic acid funtionalized SiO2Microsphere.
The quality of the metallic element containing in described water-soluble transition metal salt is that sulfonic group mesoporous silicon dioxide nano is micro-
The 5～25% of ball quality, preferably 15～20%, more preferably 20%.
The volumetric usage of described deionized water is typically calculated as with the quality consumption of sulfonic group mesoporous silicon dioxide nano microsphere
20～100mL/g.
The present invention also provides the sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere carried metal oxygen being prepared by said method
Compound catalyst.
The sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst that the present invention provides can be used for being catalyzed
Hydrogen peroxide (H2O2) catalytic oxidation in.
Further, described sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst can be used for catalysis pair
The reaction of oxygen water oxygen degradating organic dye, further, described sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere carried metal oxygen
Compound catalyst can be used for being catalyzed the reaction of hydrogen peroxide oxidation degradation of methylene blue.
The sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere that the present invention is homogeneous with duct, specific surface area is big, heat stability is good is
Carrier, by covalent bond effect, transition metal ionss is connected on the functional groups in duct, and the condition in hydro-thermal-roasting
Under, multiple transition metal ionss growth in situ in duct for the absorption are nano-metal-oxide.Because sulfonic acid funtionalized is situated between
Hole SiO2Stronger adhesion between carrier and metal ion, enhances the dispersion of nano metal cluster, hinders intergranular group
Poly-.
Compared with prior art, advantages of the present invention：With sulfonic group mesoporous silicon oxide as carrier, enhance catalyst table
Face hydrophilic and acid strength, have effectively widened the scope of application of catalyst；Sulfonic acid group promotes nano-particle in duct
Homogeneous distribution, improves the utilization rate to visible ray for the catalyst, reduces operating cost；By covalent bond by metal ion activity group
Point be connected with carrier sulfonic group, improve the conjugation of metal oxide nano particles and carrier so that catalyst have higher
Stability, multiple reuse is respond well, has good commercial Application potential quality.
Preparation method is simple of the present invention is practical, and compared with traditional catalyst, catalyst of the present invention is double in catalytic activation
Good catalysis activity is shown, not only catalyst amount is few, reaction condition is gentle, and can be multiple in oxygen water oxidation reaction
Recycle.
Brief description
Fig. 1 is the sulfonic group mesoporous silicon dioxide nano microsphere SEM and TEM electromicroscopic photograph that the embodiment of the present invention 1 is obtained, its
In (a) figure be SEM photograph, (b) figure is TEM photo.
Fig. 2 is the FTIR figure of the sulfonic group mesoporous silicon dioxide nano microsphere that the embodiment of the present invention 1 is obtained.
Fig. 3 is the mesoporous SO of CuO/ that the embodiment of the present invention 1 is obtained3H-SiO2The TEM electromicroscopic photograph of microsphere.(a) in Fig. 3
Figure and (b) figure are the TEM photo amplifying different multiples.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail in, but the present invention is not limited to following embodiments,
Without departing from present invention and scope, change all should be included in the technical scope of the present invention.
Required reagent in catalyst preparation：Tetraethyl orthosilicate (AR) Meixing Chemical Co., Ltd., Shanghai, 3- aminopropyl three
Ethoxysilane (AR) Chemical Reagent Co., Ltd., Sinopharm Group, N- sodium lauroyl sarcosine (AR) Chinese medicines group chemical reagent has
Limit company, concentrated hydrochloric acid Quzhou Ju Hua reagent company limited, dehydrated alcohol (AR) Meixing Chemical Co., Ltd., Shanghai, chlorosulfonic acid (>=
97.0%) Chemical Reagent Co., Ltd., Sinopharm Group, dichloromethane (AR) Meixing Chemical Co., Ltd., Shanghai, sodium hydroxide (AR)
Shanghai is by force along chemical reagent company limited, hydrogen peroxide (AR) Chemical Reagent Co., Ltd., Sinopharm Group, manganese acetate (AR) Shanghai
Shi Sihewei Chemical Co., Ltd., copper nitrate (AR) Shishewei Chemical Co., Ltd., Shanghai.
Embodiment 1：
Mesoporous SiO2The sulfonic acid funtionalized preparation of Nano microsphere：
0.7042g N- sodium lauroyl sarcosine (Sar-Na) is completely dissolved in the dilute HCl solution of 80ml, and (concentration of HCl is
0.1mol/L)；3ml tetraethyl orthosilicate (TEOS) and 0.25ml 3- aminopropyl triethoxysilane mixture are added above-mentioned molten
In liquid, it is subsequently poured into reactor and stands 15h in 60 DEG C of baking ovens.The product obtaining is centrifuged, is washed with deionized rear vacuum
It is dried, the white SiO of system2Nano microsphere.
Surfactant in duct is removed using high-temperature calcination.By dried 1.0g SiO2Nano microsphere is slightly
Grind, be placed in Muffle furnace, temperature programming, to 600 DEG C of roasting 6h, obtains mesoporous SiO2Nano microsphere.
By prepared mesoporous SiO2Nano microsphere (1.0g) is totally submerged in 15ml CH2Cl2Solution, will after ultrasonic disperse
4ml chlorosulfonic acid adds in said mixture, and ultrasonic vibration reacts 0.5h under room temperature, ultrasonic condition is power 100w, frequency
53kHz, is then centrifuged for, solid washs, and in vacuum oven, obtains pulverulent solids product sulfonic group meso-porous titanium dioxide
Silicon Nano microsphere, referred to as mesoporous SO3H-SiO2Microsphere.
To mesoporous SO3H-SiO2Microsphere sample carries out surface analysis, and BET specific surface area is 321m2/g；Using Flied emission
Environmental scanning electron microscope is clearly observable sulfonic acid funtionalized and does not destroy the monodisperse status of Nano microsphere (as shown in Figure 1,
In Fig. 1, (a) figure is SEM photograph, (b) figure is TEM photo), in 200-300nm, microsphere aperture is in 8-10nm for microsphere diameter
Between be meso-hole structure, be apparent that sulfonic acid group is distributed in SiO from FTIR result2In microsphere (as shown in Figure 2).
The mesoporous SO of CuO/3H-SiO2The preparation of microsphere：
By mesoporous for above-mentioned 1.0g SO3H-SiO2Microsphere sample is dispersed in 100mL deionized water, adds 0.755g tri- liquid glauber salt
Sour copper solid (copper ion mass fraction accounts for carrier 20%), is transferred to after stirring in hydrothermal reaction kettle, at a temperature of being placed on 60 DEG C
Standing 8h.After cooling, centrifugation, the cleaning of solid deionized water, are placed in vacuum oven；Slightly ground with mortar after taking-up
Mill, is placed in Muffle furnace, temperature programming, to 180 DEG C of roasting 6h, obtains solid sample sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere
Metal oxide supporting catalyst, is designated as the mesoporous SO of CuO/3H-SiO2Microsphere.
SO mesoporous to CuO/3H-SiO2Microsphere sample carries out surface analysis, and BET specific surface area is 175m2/ g, shows gold
Belong to oxide to have loaded in the duct of carrier；Using high power transmission microscopy, catalyst pattern is characterized, result such as Fig. 3
Shown, after load mesoporous sulfonic group SiO2The shape of Nano microsphere is not destroyed, and in the presence of sulfonic group in duct, promotees
Metal oxide active component is made equably to be dispersed in the duct of meso-porous nano silicon microsphere.
ICP detects the mesoporous SO of CuO/3H-SiO2In microsphere, the Cu content of load is 6.5%.Embodiment 2：
MnO2/ mesoporous SO3H-SiO2The preparation of microsphere：
The mesoporous SO of 1.0g prepared by embodiment 13H-SiO2Microsphere sample is dispersed in 100mL deionized water, adds
0.629g Glacial acetic acid manganese solid (manganese ion mass fraction accounts for carrier 20%), is transferred to after stirring in reactor, is placed on 60
8h is stood at a temperature of DEG C.After cooling, centrifugation, the cleaning of solid deionized water, are placed in vacuum oven；With grinding after taking-up
Alms bowl slightly grinds, and is placed in Muffle furnace, and temperature programming, to 180 DEG C of roasting 6h, obtains solid sample MnO2/ mesoporous SO3H-SiO2Micro-
Ball.
Embodiment 3：
Cu2-xMnxO3Loaded mesoporous SO3H-SiO2The preparation of Nano microsphere：
With prepared SO in embodiment 13H-SiO2Meso-porous nano microsphere is carrier, and 1.0g carrier is dispersed in 100mL
In deionized water, (mol ratio of Cu and Mn is 2 to add 0.528g nitrate trihydrate copper and 0.189g Glacial acetic acid manganese solid:1, gold
Belong to total mass of ion fraction and account for carrier 20%), it is transferred to after stirring in reactor, at a temperature of being placed on 60 DEG C, stand 8h.Cooling
Centrifugation, the cleaning of solid deionized water, are placed in vacuum oven afterwards；Slightly ground with mortar after taking-up, be placed in Muffle
In stove, temperature programming, to 180 DEG C of roasting 6h, obtains pulverulent solids sample Cu2-xMn0.5xO2/SO3H-SiO2Microsphere.
Comparative example 1
CuO or MnO2Or Cu2-xMn0.5xO2/ mesoporous SiO2The preparation of microsphere：
With prepared mesoporous SiO in embodiment 12Nano microsphere sample is carrier, respectively 3 parts of 1.0g support dispersion exists
In 100mL deionized water, be separately added into 0.755g nitrate trihydrate copper, 0.629g Glacial acetic acid manganese, 0.528g nitrate trihydrate copper and
0.189g Glacial acetic acid manganese (metal ion mass fraction accounts for carrier 20%), is transferred in reactor, at a temperature of being placed on 60 DEG C
Standing 8h.Eccentric cleaning after cooling, is placed in vacuum oven；Slightly ground with mortar after taking-up, be placed in Muffle furnace,
Temperature programming to 180 DEG C of roasting 6h, obtain pulverulent solids sample CuO/SiO2Microsphere, MnO2/SiO2Microsphere, Cu2- xMn0.5xO2/SiO2Microsphere.
ICP detects CuO/SiO2In microsphere, the Cu content of load is the mesoporous SO of CuO/ in 2.9%, with embodiment 13H-SiO2
In microsphere, the Cu content of load is 6.5% contrast it is seen that mesoporous SiO2Carrier, after sulfonic acid funtionalized, substantially increases to metal
The load capacity of ion.
Embodiment 4：
Metal-oxide/mesoporous SO with the preparation of embodiment 1-33H-SiO2Prepared metal oxygen in microsphere and comparative example 1
Compound/mesoporous SiO2Nanospheres are catalyst, test its catalytic performance to hydrogen peroxide oxidation degradation of methylene blue.Logical
Cross H in calculating analysis decoloring dye waste water rate, total organic carbon (TOC) clearance and reactor2O2Decomposition efficiency evaluating work(
SiO can be changed2The carrier and Metal Ion Selective Electrode affecting laws to catalytic performance.
Catalysis activity H2O2The experimental procedure of light degradation reactive dye：Prepare the methylene that 100ml concentration is 100mg/L first
Base indigo plant dye solution, adjusts the pH to 6.0 of reactant liquor with dilute hydrochloric acid or sodium hydroxide；Then weighing catalyst, to be added to dyestuff molten
In liquid, the concentration making catalyst in dye solution is 0.5g/L, and catalyst is mixed homogeneously with solution, is placed in 25 by ultrasonic disperse
In DEG C constant temperature oscillation case, before photocatalytic degradation experiment is carried out, first reactant liquor is vibrated under the conditions of lucifuge 30min and urged with reaching
The adsorption equilibrium of agent；Light source is placed in superjacent, opens visible lamp (light source selects 150W sodium vapor lamp), add 4.98mmol
H2O2, start degradation experiment under conditions of visible ray.Degradation time is 120min, in Oxidative Degradation Process, according to certain
Time interval is drawn reactant liquor and is analyzed testing H2O2Concentration, absorbance and TOC concentration.Calculate percent of decolourization, TOC goes
Except rate and H2O2Resolution ratio, acquired results are as shown in table 1.
As shown in Table 1, mesoporous SiO2Carrier can effectively improve the activity of catalyst after sulfonic acid funtionalized；The double gold of Cu/Mn
The activity belonging to oxide carried type catalyst will be substantially better than single metal oxides loaded catalyst.
The Performance comparision of table 1 loaded catalyst
Claims (8)
1. a kind of preparation method of sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst it is characterised in that
The method comprising the steps of：
(1) tetraethyl orthosilicate and co-structured directed agents are added to dissolved with the hydrochloric acid solution of anion surfactant, heat
50～120 DEG C of reaction 10～36h, after the completion of reaction, centrifugation, solid washing, vacuum drying obtain SiO2Nano microsphere；SiO2Receive
Meter Wei Qiu is in 400～800 DEG C of temperature lower calcination 4～8h, prepared mesoporous silicon dioxide nano microsphere；
Described co-structured directed agents are 3- aminopropyl triethoxysilane, and described anion surfactant is N- lauroyl flesh ammonia
Sour sodium or dodecylbenzene sodium sulfonate；
(2) the mesoporous silicon dioxide nano microsphere preparing step (1) is immersed in dichloromethane, after ultrasonic disperse, adds chlorine
Sulfonic acid, is reacted under ultrasonic vibration, reacts 0.5～3h under room temperature, and after the completion of reaction, centrifugation, solid washing, vacuum are done
Dry, prepared sulfonic group mesoporous silicon dioxide nano microsphere；Described mesoporous silicon dioxide nano microsphere, the mass ratio of chlorosulfonic acid are 1：
2～15；
(3) sulfonic group mesoporous silicon dioxide nano microsphere prepared by step (2) is added deionization with water-soluble transition metal salt
In water, after stirring and evenly mixing, carry out hydro-thermal reaction, at a temperature of being heated to 50～150 DEG C, react 4～20h, after the completion of reaction, centrifugation,
Solid cleans, vacuum drying, and gained solid product is placed in Muffle furnace, and 150～600 DEG C of temperature lower calcination 2～6h prepare
Sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst；The gold containing in described water-soluble transition metal salt
The quality belonging to element is the 5～25% of sulfonic group mesoporous silicon dioxide nano microspheres quality；
Described water-soluble transition metal salt is the nitrate of transition metal and/or acetate, described transition metal is Fe, V, Ni,
A kind of or two kinds in Cu, Co, Mn.
2. the method for claim 1 is it is characterised in that in described step (1), described tetraethyl orthosilicate, co-structured guiding
Agent, the ratio of the amount of the material of anion surfactant are 100：4～12：4～40.
3. the method for claim 1 is it is characterised in that in described step (1), described dissolved with anion surfactant
Hydrochloric acid solution be by anion surfactant be dissolved in dilute hydrochloric acid prepare obtain, in dilute hydrochloric acid the concentration of HCl be 0.05～
0.2mol/L, the concentration dissolved with anion surfactant in the hydrochloric acid solution of anion surfactant is 20～50mmol/
L.
4. the method for claim 1 is it is characterised in that in described step (3), described water-soluble transition metal salt is nitre
One of sour copper, manganese acetate or two kinds.
5. the method for claim 1 is it is characterised in that in described step (3), the temperature of hydro-thermal reaction is 60 DEG C, reaction
Time is 8h.
6. the sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere gold-supported that the method as described in one of Claims 1 to 5 prepares
Belong to oxide catalyst.
7. sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst as claimed in claim 6 is double in catalysis
Application in the reaction of oxygen water catalytic oxidizing.
8. sulfonic acid funtionalized mesoporous silicon dioxide micro-sphere metal oxide supporting catalyst as claimed in claim 6 is double in catalysis
Application in the reaction of oxygen water oxygen degradating organic dye.
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| CN106007125A (en) * | 2016-07-08 | 2016-10-12 | 重庆交通大学 | Dye wastewater treatment technology |
| CN108624317B (en) | 2018-07-12 | 2023-02-17 | 京东方科技集团股份有限公司 | Core-shell quantum dot and preparation method and application thereof |
| CN110313470A (en) * | 2019-07-04 | 2019-10-11 | 安徽大学 | A kind of preparation method of grafted guanidine salt polymer hollow mesoporous silicon oxide antibacterial agent |
| CN111266103A (en) * | 2020-01-17 | 2020-06-12 | 华东理工大学 | Synthesis method of nano silicon sphere reactor and application of nano silicon sphere reactor in organic dye wastewater |
| CN111704229B (en) * | 2020-06-22 | 2022-03-04 | 东南大学 | Preparation method of nano low-dimensional catalyst for degrading acrylic fiber wastewater and degradation method |
| CN113244934B (en) * | 2021-05-25 | 2022-11-08 | 上海华谊（集团）公司 | Catalyst for producing 2,3,6-trichloropyridine and preparation method thereof |
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| CN102992329A (en) * | 2011-09-15 | 2013-03-27 | 同济大学 | Method for preparing mesoporous silicon oxide microspheres |
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