CN101632943B - Porous material externally loaded TiO2-X/Csurf. composite and preparation process - Google Patents
Porous material externally loaded TiO2-X/Csurf. composite and preparation process Download PDFInfo
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- CN101632943B CN101632943B CN2009100435233A CN200910043523A CN101632943B CN 101632943 B CN101632943 B CN 101632943B CN 2009100435233 A CN2009100435233 A CN 2009100435233A CN 200910043523 A CN200910043523 A CN 200910043523A CN 101632943 B CN101632943 B CN 101632943B
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Abstract
The present invention relates to a porous material externally loaded TiO2-X/Csurf. composite and a preparation process. The supercritical fluid precipitation technology and the sol-gel method are adopted to prepare the composite nanomaterial TiO2-X/Csurf. (X: transition metal; Csurf.: carbon surface) with an external load structure. The preparation process is characterized in that the composite externally loaded TiO2-X/Csurf. prepared by the supercritical pretreatment and the sol-gel method has novel structure and good chemical and physical properties. The preparation process provides a new method for the applied research of porous material externally loaded and doped TiO2 type photocatalytic material. Meanwhile, the process is simple and is applicable to industrialized production and makes a positive contribution to developing the studying theory, technology and method system of the material externally loaded nanomaterial.
Description
Technical field
The present invention relates to porous material externally loaded TiO
2-X/C
Surf.Complex and preparation technology thereof belong to field of functional materials.
Background technology
TiO
2Because of its biologically inert and chemical inertness, photoetch and chemical attack can not take place, advantage such as cheap, and a kind of photochemical catalyst that is proved to be to be most widely used.Because TiO
2Electron distributions be characterised in that the existence that band gap is arranged between its conduction band and the valence band.When being subjected to illumination, as long as the energy of photon equals or exceeds semi-conductive band-gap energy (hv 〉=E
g), just can make electronics transit to conduction band, thereby produce conduction band electron and valence band hole from valence band.Under the electric field action of space charge layer, the free electron of conduction band is moved to semiconductive particles surface rapidly and is transferred to oxidation component in the solution, thereby light induced electron and hole form hydroxyl radical free radical OH through series reaction, and it can the nearly all organic matter of oxidation.Therefore, it (is handled as waste water and gas) in the environmental protection field and has powerful application prospect.Course of reaction is as follows:
TiO
2+hv→h
++e
-
H
2O+h
+→·OH+H
+
e
-+O
2→O
2 -·
H
++O
2 -·→HO
2·
2HO
2·→H
2O
2+O
2
H
2O
2+O
2 -·→·OH+OH
-+O
2
h
++OH
-→·OH
h
++ org → intermediate → CO
2+ H
2O
OH+org → intermediate → CO
2+ H
2O
Yet, because TiO
2Greater band gap (about 3.2eV), the threshold wave-length of its absorption are less than 400nm, and be not high to the utilization rate of sunshine; Influenced TiO
2The practicability and the industrialization process of multiphase photocatalysis reaction.Discover, by transient metal doped or conductor oxidate is compound can improve TiO
2Photocatalytic activity and visible light utilization rate.Therefore, nano-TiO
2(X: transition metal) the doping catalysis material also just becomes one of research focus of photocatalysis field to-X.But, the TiO of preparation
2-X nano-powder, nanofiber because particle is trickle, are reunited in the aqueous solution, free settling not easily, and catalyst is difficult to separate and reclaims, and the loss of catalyst activity composition is big, is unfavorable for the regeneration of catalyst and utilization again; Nano thin-film is because its specific area is smaller, and photocatalytic activity and photocatalysis efficiency are not high, also influences and limited its practical application.For this reason, in recent years to the preparation of adulterated TiOx photochemical catalyst and the great attention that Photocatalytic Performance Study has been subjected to people with support structures.Porous charcoal becomes a kind of desirable carrier material because of having characteristics such as stable chemical performance, cheap, absorption affinity appropriateness in titania oxide supportedization research.But up to now, a large amount of work also mainly concentrates on titanium oxide deposition and prepares the aspect in porous material.We know, TiO
2Only be subjected to just having photocatalytic activity after the illumination activation, and a little less than the penetration capacity of ultraviolet light.Therefore, the intrapore TiO of charcoal
2Be not possess photocatalytic activity; In addition, TiO
2Be deposited in the hole, the specific area of carrier is descended, slackened the effect that adopts the load increasing specific surface area to strengthen catalytic activity, influence and restricted its suitability for industrialized production and practical application.But it is worth noting, also do not prepare the outer load TiO of porous material (charcoal) so far
2The effective ways of-X composite Nano catalysis material.
Summary of the invention
Technical problem to be solved by this invention is: solve the problem that above-mentioned prior art exists, and provide that a kind of anti-microbial property is good, avirulence, specific area is big, intensity is high, processing technology is good, preparation technology is simple, be easy to the porous material externally loaded TiO of suitability for industrialized production
2-X/C
Surf.Complex and preparation technology thereof.
The technical solution used in the present invention is: by super dissolubility, strong diffusivity and the unique mass transfer performances that fluid has, make the solute dissolving form supersaturated solution, separate critical condition and cause its crystalline deposit; Utilize this method with supercritical CO
2Fluid is a solvent, is template with the porous material, and low-molecular-weight organic solution is penetrated in the hole,, realizes to the shutoff of porous material hole the preparation porous material then through coagulating sedimentation---low molecule shutoff carrier; As the bimodulus plate, colloidal sol---gel method is prepared TiO in employing then
2-X colloidal sol body loads on the shutoff carrier surface, again by Low Temperature Heat Treatment, the outer load TiO of high-temperature roasting poromerics
2-X/Csurf complex.
In the technique scheme, concrete preparation technology is:
(1) by the supercritical fluid precipitation process, low molecule organic solution is penetrated in the porous material hole, remove critical condition and make its precipitation, preparation porous material-low molecule shutoff carrier;
(2) being initiation material with the butyl titanate, is that solvent, diethanol amine are chelating agent with the absolute ethyl alcohol, under the interaction of distilled water, concentrated hydrochloric acid, and synthetic TiO
2-X colloid;
(3) make TiO by sol-gel process
2Or TiO
2The precursor sol of-X is coated on porous material-low molecule shutoff carrier, preparation TiO
2-X presoma/C
Surf.Composite;
(4) by high-temperature roasting TiO
2-X presoma/C
Surf.Composite obtains TiO
2/ C
Surf., TiO
2-Fe/C
Surf., TiO
2-Ag/C
Surf., TiO
2-Mn/C
Surf., TiO
2-Cu/C
Surf., TiO
2-Cr/C
Surf.Deng TiO
2-X/Csurf. composite nano materials;
X is a transition metal in the above-mentioned formula, and Csurf is a carbon surface.
In the technique scheme, the agents useful for same percentage by weight is: butyl titanate, purity＞99.0,50-65%; Diethanol amine, purity＞99.9,1-5%; Absolute ethyl alcohol, purity＞99.9,25-35%; Poly-diethanol, purity＞99.9,2-8%.
In the technique scheme, porous material is active carbon, aluminium oxide, silica, zeolite.
In the technique scheme, low molecular compound is isobutanol, stearic acid, paraffin, several alkane of ring.
In the technique scheme, super critical condition, heating rate 2-4 ℃, temperature 34.1-300 ℃, pressure 7.1-50MPa.
In the technique scheme, separate critical condition, at first stop heating, allow overcritical still cool off, reaching temperature is the following temperature of low molecular compound freezing point.
In the technique scheme, the inorganic matter presoma of X is ferric nitrate, silver nitrate, cerous nitrate, copper nitrate, zirconium nitrate, zinc nitrate, manganese nitrate etc.
In the technique scheme, TiO
2Or TiO
2The precursor sol of-X is coated on porous material-low molecule shutoff carrier: porous material-low molecule shutoff carrier is put into TiO
2Or TiO
2In-X colloidal sol the body,, the colloidal sol body is coated on the shutoff carrier surface, applies number of times 1-8 time, ultrasonic time 10-300min then by ultrasonic shock effect.
In the technique scheme, before the roasting, TiO
2-X presoma/C
Surf.The temperature of heat-treating is 100-300 ℃, and time 1-3h, heating rate are 0.5-3 ℃/min.
In the technique scheme, sintering temperature is 300-1000 ℃, and time 1-3h, heating rate are between the 0.5-3 ℃/min.
In the technique scheme, described template is made of the identical a kind of material of composition, and described bimodulus plate is combined through physical method by two kinds of different materials of composition and constituted.
Know-why:
Supercritical fluid has two-phase (gas phase, liquid phase) character, and therefore, the solute of high-dissolvability evenly distributes in liquid and gas, and gas phase have a very strong flowability, is that solute Distribution is more even.When supercritical fluid under certain conditions makes solution reach high degree of supersaturation and supersaturation speed, thereby but rapid precipitation goes out the littler particulate of particle size that obtains than conventional method, in addition, by regulating operating parameter, technology is the crystallization control process more accurately, the size distribution of control product forms the little and size distribution of average grain diameter.
The characteristics of supercritical fluid sedimentation: particularly nano particle is in the successful Application of high-technology field along with ultrafine dust, and the preparation of ultrafine dust has become the focus that people pay close attention to.Past has developed and has formed some routine techniques and be used to prepare ultrafine particle.These methods are owing to the shortcoming that exists is separately restricting its application.Be the particle size distribution wide (0.5-25um) that forms and have only a fraction of particle to belong to nanometer range as spray-drying, ultrafine-milled major defect.CO
2Supercritical temperature: 34.1, pressure: 7.1MPa
Colloidal sol---gel process: under normal temperature or approximate normal temperature, metal alkoxide solution is added water decomposition, polycondensation reaction takes place simultaneously make colloidal sol, more further reaction form gel and and then solidify, obtain the method for inorganic material then through Low Temperature Heat Treatment.
Advantage:
1. operating temperature is far below the glass melting temperature, and energy savings makes the material preparation process be easy to control;
2. between each component of Zhi Bei material highly evenly, compositing range is wide and can change significantly;
3. technology is simple, is easy to industrialization, and cost is low, applying flexible;
4. can enhance productivity;
5. can guarantee the purity of final products;
6. Zhi Bei aeroge is the nano-meter porous amorphous solid-state material of the controlled novel light of a kind of structure, has many special natures, thereby is containing wide application prospect.
Therefore, TiO
2Loading on porous material surface outward is to solve photocatalysis technology to be applied to sewage degradation treatment effective method the most.Utilize TiO
2-X/C
Surf.The nanometer micropore characteristic that composite has, high-specific surface area characteristic, concerted catalysis characteristic, in conjunction with the heterogeneous interface effect of this doping system and quantum size effect, the quantum confined effect of low-dimension nano material, outer support structures obtains to have high activity, separate easily and reusable novel photocatalysis TiO
2-X/C
Surf.Composite.Simultaneously, this technology is simple, is easy to suitability for industrialized production.
The present invention adopts overcritical preconditioning technique and sol-gel process, by heat treatment and the outer load TiO of high-temperature roasting poromerics
2-X complex.At present, we utilize this technology to prepare TiO
2/ C
Surf., TiO
2-Fe/C
Surf., TiO
2-Ag/C
Surf., TiO
2-Mn/C
Surf., TiO
2-Cu/C
Surf., TiO
2-Cr/C
Surf.Deng composite nano materials.Porous material externally loaded TiO
2-X complex has following remarkable advantage effect: (a) have high anti-microbial property, do not have any toxicity; (b) specific area is big, and pore structure can be adjusted, and can carry out Quantitative design; (c) intensity height, cohesive force is strong, and processing technology is good; (d) baking temperature is low, and preparation technology is simple, and production cost is low, is easy to suitability for industrialized production; (e) being widely used, is to solve photocatalysis technology to be applied to sewage degradation treatment effective method the most, has saved sewage degradation treatment cost.
TiO
2-X/C
Surf.The complex physical and chemical performance
Porous material externally loaded TiO
2-X complex is after 500 ℃ of heat treatment, and its crystalline structure is an anatase, and crystallite dimension is between 20-60nm.Under the low power Electronic Speculum, TiO
2-X/C
Surf.The complex surfaces pattern is more even, and hole is arranged, under the high power Electronic Speculum, and TiO
2-X/C
Surf.Few surface defects only contains very a spot of impurity; Near 380nm, produce tangible UV absorption turning simultaneously.TiO
2The optical absorption band edge of fiber is greatly about 380nm, and there is strong absorption band in the ultraviolet light zone between 200nm-380nm, with TiO
2Material powder is compared, TiO
2The optical absorption band edge of nanofiber does not obviously change.
TiO
2-X/C
Surf.Complex has certain intensity, high specific area.Through 500 ℃ of heat treated fibers, its organic matter almost decomposes fully, and the O-H linkage content is higher relatively, and this is mainly due to due to the outer load moisture that complex surfaces absorbs.
Description of drawings
Fig. 1 is preparation technology's schematic diagram of the present invention
Fig. 2 is TiO
2/ C
Surf.The complex stereoscan photograph
Fig. 3 is TiO
2/ C
Surf.The X-ray diffractogram of complex under treatment of different temperature
Fig. 4 is TiO
2/ C
Surf.The infared spectrum of complex
The specific embodiment:
1) TiO
2The colloidal sol preparation method is: with the butyl titanate is initiation material, is that solvent, diethanol amine are chelating agent with the absolute ethyl alcohol, under the interaction of distilled water, concentrated hydrochloric acid, synthesizes TiO by hydrolysis and polycondensation reaction
2Colloidal sol.The diethanol amine chelating agent at first adds in the there-necked flask with butyl titanate and diluent absolute ethyl alcohol, and distilled water and hydrochloric acid and absolute ethyl alcohol add simultaneously by funnel, and both rate of addition generally are controlled at 0.7-1.0mlmin
-1Between.
2) also join in the there-necked flask by the inorganic matter presoma of above-mentioned prescription, adopt sol-gel process to prepare TiO X
2-X colloidal sol body;
3) porous material is put into a two-layer framework with holes, insert then in the overcritical still, in fill low-molecular-weight organic matter such as isobutanol, stearic acid, paraffin, several alkane of ring etc., heating rate 2-4 ℃, be raised to appropriate temperature range (34.1-300 ℃) and reach under the appropriate pressure range (7.1-50MPa), keep 2-4h, low-molecular-weight organic matter is deposited in the hole of porous material fully;
4) after low-molecular-weight organic matter is deposited on the hole of porous material fully, stop heating, allow overcritical still cool off, reach temperature and be low molecular compound freezing point temperature once, higher as room temperature, can adopt the ice bath cooling.Take out porous material-low molecule shutoff carrier then;
5) porous material-low molecule shutoff carrier is put into titanium colloidal sol body,, the colloidal sol body is coated on the shutoff carrier surface, apply number of times 1-8 time, ultrasonic time 10-300min then by ultrasonic shock effect.
6) before the roasting, TiO
2-X presoma/C
Surf.Heat-treat, temperature 100-300 ℃, time 1-3h, heating rate are 0.5-3 ℃/min;
7) to porous material externally loaded TiO
2-X complex carries out high-temperature roasting, and temperature 300-1000 ℃, time 1-3h, heating rate are 0.5-3 ℃/min;
8) to porous material externally loaded TiO
2The chemical form of-X complex specific area, aperture, crystal formation, surface topography, element etc. carries out test analysis;
The porous material externally loaded TiO of preparation
2-X complex, in air through being pure anatase crystal behind 500 ℃ of heat treatment 1-2h.
Embodiment 1: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 300 ℃ according to 2 ℃/min of heating rate, after pressure is 7.1MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.In addition, adopting sol-gel process, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 4g distilled water, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Colloidal sol.Secondly, the porous material-low molecule shutoff carrier that obtains is put into TiO
2In the colloidal sol body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 1 time, ultrasonic time 10min.At last with TiO
2Presoma/C
Surf.Heat-treat, 100 ℃ of temperature, time 3h, heating rate are 0.5 ℃/min; And then carry out roasting, 300 ℃ of temperature, time 3h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area is 884m
2/ g, TiO
2Nano particle loads on porous material surface.
Embodiment 2: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 300 ℃ according to 4 ℃/min of heating rate, after pressure is 12MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.Adopting sol-gel process, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol and 2g ferric nitrate mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 4g distilled water, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Secondly-Fe colloidal sol, put into TiO with the porous material-low molecule shutoff carrier that obtains
2In-Fe colloidal sol the body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 3 times, ultrasonic time 10min.At last with TiO
2-X presoma/C
Surf.Heat-treat, 300 ℃ of temperature, time 1h, heating rate are 3 ℃/min; And then carry out roasting, 1000 ℃ of temperature, time 1h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area reaches 568m
2/ g, TiO
2-Fe nano particle loads on porous material surface.
Embodiment 3: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 180 ℃ according to 2 ℃/min of heating rate, after pressure is 15MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.Adopting sol-gel method, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 10g distilled water and 2g copper nitrate, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Secondly-Cu colloidal sol, put into TiO with " porous material-low molecule " the shutoff carrier that obtains
2In-Cu colloidal sol the body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 1 time, ultrasonic time 10min.At last with TiO
2-X presoma/C
Surf.Heat-treat, 150 ℃ of temperature, time 1h, heating rate are 1 ℃/min; And then carry out roasting, 500 ℃ of temperature, time 2h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area reaches 1128m
2/ g, TiO
2-Cu nano particle loads on porous material surface.
Embodiment 4: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 34.1 ℃ according to 2 ℃/min of heating rate, after pressure is 50MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.Adopting sol-gel method, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 10g distilled water and zinc nitrate, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Secondly-Zn colloidal sol, put into TiO with the porous material-low molecule shutoff carrier that obtains
2In-Zn colloidal sol the body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 1 time, ultrasonic time 10min.At last with TiO
2-X presoma/C
Surf.Heat-treat, 150 ℃ of temperature, time 2h, heating rate are 1 ℃/min; And then carry out roasting, 800 ℃ of temperature, time 2h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area reaches 938m
2/ g, TiO
2-Zn nano particle loads on porous material surface.
Embodiment 5: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 34.1 ℃ according to 3 ℃/min of heating rate, after pressure is 8MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.Adopting sol-gel method, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 10g distilled water and chromic nitrate, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Secondly-Cr colloidal sol, put into TiO with the porous material-low molecule shutoff carrier that obtains
2In-Cr colloidal sol the body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 1 time, ultrasonic time 10min.At last with TiO
2-X presoma/C
Surf.Heat-treat, 300 ℃ of temperature, time 1h, heating rate are 0.5 ℃/min; And then carry out roasting, 300 ℃ of temperature, time 3h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area reaches 834m
2/ g, TiO
2-Cr nano particle loads on porous material surface.
Embodiment 6: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 300 ℃ according to 2 ℃/min of heating rate, after pressure is 7.1MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.Adopting sol-gel method, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 4g distilled water and cerous nitrate, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Secondly colloidal sol, put into TiO with the porous material-low molecule shutoff carrier that obtains
2In-Fe colloidal sol the body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 1 time, ultrasonic time 10min.At last with TiO
2-X presoma/C
Surf.Heat-treat, 300 ℃ of temperature, time 1h, heating rate are 1 ℃/min; And then carry out roasting, 1000 ℃ of temperature, time 1h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area reaches 162m
2/ g, TiO
2-Ce nano particle loads on porous material surface.
Embodiment 7: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 160 ℃ according to 2 ℃/min of heating rate, after pressure is 13MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.Adopting sol-gel method, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 12g distilled water and manganese nitrate, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Secondly-Mn colloidal sol, put into TiO with the porous material-low molecule shutoff carrier that obtains
2In-Mn colloidal sol the body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 5 times, ultrasonic time 10min.At last with TiO
2-X presoma/C
Surf.Heat-treat, 150 ℃ of temperature, time 1h, heating rate are 1 ℃/min; And then carry out roasting, 500 ℃ of temperature, time 2h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area reaches 781m
2/ g, TiO
2-Mn nano particle loads on porous material surface.
Embodiment 8: at first the 15g activated coco nut charcoal is put in the shelf of overcritical still, and isobutanol 20ml is arranged in the autoclave, is warmed up to 130 ℃ according to 2 ℃/min of heating rate, after pressure is 11MPa, keeps 2h; With overcritical still cool to room temperature, obtain porous material-low molecule shutoff carrier then.Adopting sol-gel method, is after 99.0% butyl titanate, 3g diethanol amine and 10g absolute ethyl alcohol mix, to join in the there-necked flask with 60g purity, stirs evenly with GS122 type electronics constant speed stirrer.The absolute ethyl alcohol of getting 20g mixes with 4g distilled water and 3g silver nitrate, slowly splashes in the there-necked flask by separatory funnel then.Butyl titanate forms TiO by hydrolysis, condensation reaction
2Secondly-Ag colloidal sol, put into TiO with the porous material-low molecule shutoff carrier that obtains
2In-Ag colloidal sol the body, in ultrasonic vibrations process, it is coated in the shutoff carrier surface, applies number of times 1 time, ultrasonic time 10min.At last with TiO
2-X presoma/C
Surf.Heat-treat, 200 ℃ of temperature, time 1h, heating rate are 1 ℃/min; And then carry out roasting, 600 ℃ of temperature, time 2h under the nitrogen protection.Its crystal formation is an anatase, and nano particle is of a size of 30-50nm, and specific area reaches 1268m
2/ g, TiO
2-Ag nano particle loads on porous material surface.
Claims (1)
1. porous material externally loaded TiO
2-X/C
Surf.The preparation technology of complex by super dissolubility, strong diffusivity and the unique mass transfer performances that fluid has, makes the solute dissolving form supersaturated solution, separates critical condition and causes its crystalline deposit; Utilize this method with supercritical CO
2Fluid is a solvent, is template with the porous material, and low-molecular-weight organic solution is penetrated in the hole,, realizes to the shutoff of porous material hole the preparation porous material then through coagulating sedimentation---low molecule shutoff carrier; As the bimodulus plate, colloidal sol---gel method is prepared TiO in employing then
2-X colloidal sol body loads on the shutoff carrier surface, again by Low Temperature Heat Treatment, the outer load TiO of high-temperature roasting poromerics
2-X/Csurf complex; It is characterized in that concrete preparation technology is:
(1) by the supercritical fluid precipitation process, low molecule organic solution is penetrated in the porous material hole, remove critical condition and make its precipitation, preparation porous material-low molecule shutoff carrier;
(2) being initiation material with the butyl titanate, is that solvent, diethanol amine are chelating agent with the absolute ethyl alcohol, under the interaction of distilled water, concentrated hydrochloric acid, and synthetic TiO
2-X colloid;
(3) make TiO by sol-gel process
2The precursor sol of-X is coated on porous material-low molecule shutoff carrier, preparation TiO
2-X presoma/C
Surf.Composite;
(4) by high-temperature roasting TiO
2-X presoma/C
Surf.Composite obtains TiO
2-Fe/C
Surf., TiO
2-Ag/C
Surf., TiO
2-Mn/C
Surf., TiO
2-Cu/C
Surf.Be TiO
2-X/C
Surf.Composite nano materials; C in the above-mentioned formula
Surf.Be carbon surface;
Above-mentioned porous material is an active carbon; Low molecular compound is isobutanol, stearic acid, paraffin, solid alcohol;
Described super critical condition: heating rate 2-4 ℃, temperature 34.1-300 ℃, pressure 7.1-50MPa; Separate critical condition: at first stop heating, allow overcritical still cool off, reaching temperature is the following temperature of low molecular compound freezing point;
The inorganic matter presoma of X is ferric nitrate, silver nitrate, copper nitrate, manganese nitrate;
Above-mentioned TiO
2The precursor sol of-X is coated on porous material-low molecule shutoff carrier: porous material-low molecule shutoff carrier is put into TiO
2In-X colloidal sol the body,, the colloidal sol body is coated on the shutoff carrier surface, applies number of times 1-8 time, ultrasonic time 10-300min then by ultrasonic shock effect;
Before the above-mentioned roasting, TiO
2-X presoma/C
Surf.The temperature of heat-treating is 100-300 ℃, and time 1-3h, heating rate are 0.5-3 ℃/min;
Above-mentioned sintering temperature is 300-1000 ℃, and time 1-3h, heating rate are between the 0.5-3 ℃/min.
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| CN104353411B (en) * | 2014-11-19 | 2016-06-08 | 上海电力学院 | The preparation method of the strong sorbent material of a kind of water treatment |
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| CN110280313B (en) * | 2019-07-11 | 2020-03-24 | 哈尔滨工业大学 | Three-dimensional structure loaded TiO2-xMethod for producing a material |
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