CN104826582A - Preparation method of graphene-mesoporous silica aerogel - Google Patents
Preparation method of graphene-mesoporous silica aerogel Download PDFInfo
- Publication number
- CN104826582A CN104826582A CN201510161956.4A CN201510161956A CN104826582A CN 104826582 A CN104826582 A CN 104826582A CN 201510161956 A CN201510161956 A CN 201510161956A CN 104826582 A CN104826582 A CN 104826582A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- silica aerogel
- meso
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a preparation method of graphene-mesoporous silica aerogel. The preparation method comprises graphite oxide synthesis, graphene oxide solution preparation, graphene-silica gel preparation, and graphene-mesoporous silica aerogel preparation. The preparation method combines excellent mesoporous structure characteristics of mesoporous silica and hydrophobicity of graphene and prepares the novel environmentally friendly adsorption material with high sewage heavy metal ion and organic pollutant selective adsorbability. Through mesoporous silica, graphene aggregation is inhibited and a high specific surface area is kept. Through graphene, mesoporous silica is uniformly dispersed and mesoporous silica stability is kept. The graphene-mesoporous silica aerogel has high composite material adsorption capability and can be easily separated from the solution after adsorption. The preparation method has simple processes. The graphene-mesoporous silica aerogel has characteristics of graphene and mesoporous silica.
Description
Technical field
The present invention relates to mesoporous material and preparing technical field thereof, specifically, relate to the preparation method of a kind of Graphene-meso-porous titanium dioxide silica aerogel.
Background technology
Metaporous silicon dioxide material has stable chemical nature, specific area is large, pore size distribution$ scope is wide and can realize the advantages such as large-scale production, can be used as adsorbent for sewage disposal.But pure silicon dioxide mesoporous material itself does not have activated centre, adsorbance is not high, the rate of adsorption is comparatively slow, limits it in this field extensive use.Therefore the concern of the research prepared of the functionalization of Metaporous silicon dioxide material, composite mesopore earth silicon material extremely people.
Chinese patent CN201010167801.9 provides a kind of preparation method of the carboxylated MCM-41 mesopore molecular sieve for Adsorption of Heavy Metal Ions.This patent for carrier with calcined MCM-41, adopts grafting after two steps, modifies with amino silicane coupling agent and halogenated acid to MCM-41.Its functional group can with some transition metal ions generation mating reaction, occur effective as selective absorption.
Chinese patent CN201210411154.0 proposes a kind of New Type of Mesoporous material preparation method adsorbing heavy metal ions in wastewater.Adopt different templates, with different silicon sources and rare earth compound for presoma, at 100 ~ 150 DEG C, crystallization forms sol-gel in 3 ~ 8 hours.By removing template, prepare ordered meso-porous silicon oxide rare earth material, and for heavy metal ion adsorbed experiment.
Chinese patent CN201310378526.9 proposes a kind of preparation method of the magnetic mesoporous silica composite material of graphene oxide of adsorbable water pollutant.First this patent adopts hydro-thermal method, at 180 ~ 210 DEG C, reacts 8 ~ 72 hours, prepares the magnetic-particle for subsequent packet silicon.Then utilize long chain alkane as pore-foaming agent, with ethyl orthosilicate generation copolymerization, then remove pore-foaming agent by heat treatment, obtain the magnetic mesoporous silicon oxide particle of surface with hydroxyl.Finally, adopt carbodiimide activation graphene oxide, obtain the magnetic mesoporous silica composite material of graphene oxide.Due to surface group, this composite can adsorb humic acid simultaneously and heavy metal ion is plumbous.
Chinese patent CN201310309667.5 provides a kind of magnetic mesoporous silica adsorbent removing Organic Pollutants In Water and preparation method thereof.First reacted in water by molysite and alkali, obtained iron hydroxide, after centrifugal, in precipitation, add glacial acetic acid, form hydrated ferric oxide colloidal solution; Then in hydrated ferric oxide colloidal solution, non-ionic polymer and silicon source presoma is added, be stirred to and mix completely, hydro-thermal reaction 2 ~ 48 hours, collect the solid product generated, dry, roasting is removed the magnetic mesoporous silica adsorbent of Organic Pollutants In Water.
Chinese patent 201410007948.X proposes the preparation method of magnetic mesoporous silicon, preparation method and magnetic mesoporous silicon adsorbent.This patent take ethyl orthosilicate as silicon source, and ferrous sulfate amine is source of iron, and F-127 block copolymer is template, prepares magnetic mesoporous silica.Be there is oxidative polymerization in acid condition in the magnetic mesoporous silicon of preparation and Ammonium Persulfate 98.5 and aniline, then wash, filter, drying obtains magnetic mesoporous silicon adsorbent.
From above method, carry out surface-functionalizedly can improving its adsorptivity to Metaporous silicon dioxide material; Add magnetic oxide, be conducive to adsorbent and reclaim.But above method all adopts hydro-thermal method when preparing mesoporous material, and equipment cost is high; And the sample of preparation is powder body material, there is the problem reclaiming difficulty.
Graphene is through sp by the carbon atom of monoatomic layer
2the two-dimensional atomic crystal that hydridization is formed, has the advantages such as mechanical strength is high, theoretical specific surface area large, obvious hydrophobicity, makes it have potential high oil-absorbing energy, containing the application prospect Worth Expecting in organic pollution sewage disposal.Although Graphene is a kind of desirable adsorbent, the lamellar structure due to Graphene easily reassembles formation graphite, reduces specific area, and is difficult to be separated from solution after absorption, normal in actual applications itself and other sorbing material is carried out compound.
Summary of the invention
The object of the invention is to overcome the defect existed in prior art, the preparation method of a kind of Graphene-meso-porous titanium dioxide silica aerogel is provided, meso-hole structure feature excellent for mesoporous silicon oxide combines with the hydrophobicity of Graphene by the method, prepare a kind of environmentally friendly sorbing material newly heavy metal ion in sewage and organic pollution to higher adsorption selection, do so on the one hand because the existence of mesoporous silicon oxide can hinder the gathering of Graphene, thus the specific area keeping it high; On the other hand because the existence of Graphene makes mesoporous silicon oxide can be uniformly dispersed, thus keep its stability.Result is that the adsorption capacity of composite is improved, and to be easily separated from solution after absorption.The method technique is simple, and the aeroge of preparation can possess the characteristic of Graphene and mesoporous silicon oxide.
Its concrete technical scheme is:
A preparation method for Graphene-meso-porous titanium dioxide silica aerogel, comprises the following steps:
Hummer ' the s method that step 1, employing are improved, is raw material with graphite, prepares graphite oxide: the reactor that the concentrated sulfuric acid and SPA are housed is placed in ice-water bath, the volume ratio 2: 1 ~ 15: 1 of the concentrated sulfuric acid and SPA, be cooled to 0 DEG C, add 1g graphite powder, in high degree of agitation, slowly add 3g KMnO
4, maintenance system temperature is no more than 20 DEG C of reaction 1h, transfers them to 35 ~ 45 DEG C of water-bath 30min.Progressively add 46mL deionized water, temperature rises to 98 DEG C and continues reaction 40min, and mixture becomes glassy yellow by sepia, with the H of 140ml deionized water and mass fraction 30%
2o
2solution-treated, neutralizes unreacted potassium permanganate, filter, with rare HCl cyclic washing filter cake to filtrate without SO
4 2-after, continue to spend deionized water to filtrate weakly acidic pH, be drying to obtain graphite oxide.
Step 2, preparation graphene oxide solution: add step 1 and obtain graphite oxide, after carrying out ultrasonic disperse, centrifugation removes unstripped graphite oxide and impurity, until form the uniform graphene oxide solution of sepia; The graphene oxide solution stable existence obtained at least 1 ~ 24 hours.
The preparation of step 3, Graphene-silica dioxide gel: the graphene oxide water solution that the NaOH aqueous solution, silicon source and step 2 are obtained, slowly be added drop-wise in softex kw (CTAB) aqueous solution of Keep agitation successively, the mol ratio of reactant is (0.12 ~ 0.25) CTAB: 1 silicon source: 0.6NaOH: 100H
2o: χ graphene oxide, reaction 1 ~ 12h, room temperature ageing, after adding reducing agent, be placed in 70 ~ 100 DEG C of baking oven reaction 1 ~ 10h, obtain hydrogel, the product obtained is washed,-70 ~-90 DEG C of drying 12 ~ 24h in vacuum freeze drier, are not removed the Graphene-aerosil of template.
The preparation of step 4, Graphene-meso-porous titanium dioxide silica aerogel: template softex kw removed by aeroge step 3 obtained, and obtains Graphene-meso-porous titanium dioxide silica aerogel.
Preferably, the supersonic frequency of ultrasonic disperse described in step 2 is 20 ~ 60KHz; The rotating speed of described centrifugation is 1000 ~ 6000 revs/min.
Preferably, the mass ratio in graphene oxide described in step 3 and silicon source is 1: 8 ~ 1: 40, and wherein, described silicon source is selected from: ethyl orthosilicate, sodium metasilicate, natural montmorillonite, saponite.
Preferably, the mass ratio of reducing agent described in step 3 and graphene oxide is 5: 1 ~ 200: 1.Wherein, described reducing agent is selected from: ascorbic acid, sodium ascorbate, sodium sulfite, sodium thiosulfate.
Preferably, the method removing template described in step 4 is roasting method, is placed in Muffle furnace by aeroge and calcines, and is warming up to 400 ~ 700 DEG C, and every 10min heats up 15 DEG C, and keeps 1 ~ 6h at such a temperature, naturally cools to room temperature.
Preferably, the method removing template described in step 4 is solvent extraction, after step 3 obtains Graphene-silica hydrogel, with EtOH/CH
3cOONa is extractant, removes softex kw; Washed by the hydrogel removing template, in vacuum freeze drier ,-70 ~-90 DEG C of drying 12 ~ 24h, obtain aeroge.
Compared with prior art, beneficial effect of the present invention is:
1. adopt different raw materials to do silicon source, reducing agent can have multiple choices, makes to prepare material variation.
2. preparation method have technique simple, with low cost, can the feature of large-scale production.
3. can improve the selective absorbing of Metaporous silicon dioxide material to organic solvent and large molecule oily matter, and the recovery of organic solvent and the Reusability of sorbing material can be realized.
4. Graphene-meso-porous titanium dioxide the silica aerogel of preparation combines the feature of Graphene, mesoporous silicon oxide and aeroge, is expected in catalyst carrier, adsorbs and be separated, be widely used in high temperature insulating protection etc.
Accompanying drawing explanation
Fig. 1 is the digital photograph of Graphene in embodiment 1-meso-porous titanium dioxide silica aerogel;
Fig. 2 is the XRD figure of Graphene in embodiment 1-meso-porous titanium dioxide silica aerogel;
Fig. 3 is the TEM figure of pure graphene aerogel;
Fig. 4 is the TEM figure of Graphene in embodiment 1-meso-porous titanium dioxide silica aerogel;
Fig. 5 is the contact picture of Graphene in embodiment 1-meso-porous titanium dioxide silica aerogel and water droplet.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in more detail.
The preparation of a kind of Graphene-meso-porous titanium dioxide silica aerogel is carried out according to the following steps:
One, adopt Hummer ' the s method improved, be raw material with graphite, prepare graphite oxide: the reactor that the concentrated sulfuric acid and SPA (volume ratio 2: 1 ~ 15: 1) are housed is placed in ice-water bath, is cooled to 0 DEG C.Add 1g graphite powder, in high degree of agitation, slowly add 3g KMnO
4, maintenance system temperature is no more than 20 DEG C of reaction 1h.Transfer them to 35 ~ 45 DEG C of water-bath 30min.Progressively add 46mL deionized water, temperature rises to 98 DEG C and continues reaction 40min, and mixture becomes glassy yellow by sepia.With the H of 140ml deionized water and mass fraction 30%
2o
2solution-treated, neutralizes unreacted potassium permanganate, with rare HCl cyclic washing filter cake to filtrate without SO
4 2-after, continue to spend deionized water to filtrate weakly acidic pH, be drying to obtain graphite oxide.
Two, prepare graphene oxide solution: add step one and obtain graphite oxide, after carrying out ultrasonic disperse, the graphite oxide that centrifugal removing is unstripped and impurity, until form the uniform graphene oxide solution of sepia; The graphene oxide solution stable existence obtained at least 1 ~ 24 hours;
The supersonic frequency of described ultrasonic disperse is 20 ~ 60KHz; The rotating speed of described centrifugation is 1000 ~ 6000 revs/min.
Three, the preparation of Graphene-aerosil: the graphene oxide water solution that the NaOH aqueous solution, silicon source and step 2 are obtained, slowly be added drop-wise in softex kw (CTAB) aqueous solution of Keep agitation successively, the mol ratio of reactant is (0.12 ~ 0.25) CTAB: 1 silicon source: 0.6NaOH: 100H
2o: χ graphene oxide, reaction 1 ~ 12h, room temperature ageing, after adding reducing agent, is placed in 70 ~ 100 DEG C of reaction 1 ~ 10h, obtains hydrogel.The product obtained washed ,-70 ~-90 DEG C of drying 12 ~ 24h in vacuum freeze drier, are not removed the Graphene-aerosil of template.
The mass ratio in described graphene oxide and silicon source is 1: 8 ~ 1: 40, and wherein, described silicon source is selected from: ethyl orthosilicate, sodium metasilicate, natural montmorillonite, saponite.
The mass ratio of described reducing agent and graphene oxide is 5: 1 ~ 200: 1.Wherein, described reducing agent is selected from: ascorbic acid, sodium ascorbate, sodium sulfite, sodium thiosulfate.
The preparation of four, Graphene-meso-porous titanium dioxide silica aerogel: template softex kw removed by aeroge step 3 obtained, and can obtain Graphene-meso-porous titanium dioxide silica aerogel.
The method one removing template is roasting method, is placed in Muffle furnace by aeroge and calcines, be warming up to 400 ~ 700 DEG C (every 10min heats up 15 DEG C), and keep 1 ~ 6h at such a temperature, naturally cool to room temperature.
The method two removing template is solvent extraction, after step 3 obtains Graphene-silica hydrogel, with EtOH/CH
3cOONa is extractant, removes softex kw; Washed by the hydrogel removing template, in vacuum freeze drier ,-70 ~-90 DEG C of drying 12 ~ 24h, obtain aeroge.
Embodiment 1
A. the synthesis of graphite oxide
The reactor of the SPA of the concentrated sulfuric acid and 2.3ml that 20.7ml is housed is placed in ice-water bath, is cooled to 0 DEG C.Add 1g graphite powder, in high degree of agitation, slowly add 3g KMnO
4, maintenance system temperature is no more than 20 DEG C of reaction 1h.Transfer them to 35 ~ 45 DEG C of water-bath 30min.Progressively add 46mL deionized water, temperature rises to 98 DEG C and continues reaction 40min, and mixture becomes glassy yellow by sepia.With the H of 140ml deionized water and mass fraction 30%
2o
2solution-treated, neutralizes unreacted potassium permanganate, with rare HCl cyclic washing filter cake to filtrate without SO
4 2-after, continue to spend deionized water to filtrate weakly acidic pH, be drying to obtain graphite oxide.
B. the preparation of graphene oxide solution
Get 200mg graphite oxide to grind, add 100mL deionized water, after ultrasonic process 30min, the removing of suspension centrifugal treating is a small amount of impurity wherein, obtains the graphene oxide solution of isotropic stable.
C. the preparation of Graphene-silica dioxide gel
Get 0.01g NaOH, 0.22g CTAB, 3.7g ethyl orthosilicate, measure the distilled water of 6ml, NaOH, CTAB are dissolved in distilled water, be made into the aqueous solution, then the NaOH aqueous solution, ethyl orthosilicate, graphene oxide solution are slowly added drop-wise to successively in the Keep agitation CTAB aqueous solution, stir 1h, room temperature ageing, after adding reducing agent 0.5g sodium ascorbate, be placed in 70 DEG C of reaction 2h, obtain hydrogel.Hydrogel ultra-pure water is replaced 10 times, to remove water-solubility impurity.
By hydrogel dry 24h in vacuum freeze drier of preparation, obtain Graphene-silica dioxide gel aeroge.
The preparation of d. Graphene-meso-porous titanium dioxide silica aerogel
Graphene-aerosil is placed in Muffle furnace and calcines, is warming up to 540 DEG C (every 10min heats up 15 DEG C), and keeps 6h at 540 DEG C, naturally cool to room temperature.Can template be removed, obtain Graphene-meso-porous titanium dioxide silica aerogel.
Embodiment 2
A. the synthesis of graphite oxide
The reactor of the SPA of the concentrated sulfuric acid and 1.9ml that 28.1ml is housed is placed in ice-water bath, is cooled to 0 DEG C.Add 1g graphite powder, in high degree of agitation, slowly add 3g KMnO
4, maintenance system temperature is no more than 20 DEG C of reaction 1h.Transfer them to 35 ~ 45 DEG C of water-bath 30min.Progressively add 46mL deionized water, temperature rises to 98 DEG C and continues reaction 40min, and mixture becomes glassy yellow by sepia.With the H of 140ml deionized water and mass fraction 30%
2o
2solution-treated, neutralizes unreacted potassium permanganate, with rare HCl cyclic washing filter cake to filtrate without SO
4 2-after, continue to spend deionized water to filtrate weakly acidic pH, be drying to obtain graphite oxide.
B. the preparation of graphene oxide solution
Get 100mg graphite oxide to grind, add 100mL deionized water, after ultrasonic process 30min, the removing of suspension centrifugal treating is a small amount of impurity wherein, obtains the graphene oxide solution of isotropic stable.
C. the preparation of Graphene-aerosil
Get 0.01g NaOH, 0.22g CTAB, 3.7g ethyl orthosilicate, measure the distilled water of 6ml, NaOH, CTAB are dissolved in distilled water, be made into the aqueous solution, then the NaOH aqueous solution, ethyl orthosilicate, graphene oxide solution are slowly added drop-wise to successively in the Keep agitation CTAB aqueous solution, stir 1h, room temperature ageing, after adding reducing agent 0.25g sodium ascorbate, be placed in 70 DEG C of reaction 2h, obtain hydrogel.Hydrogel ultra-pure water is replaced 10 times, to remove water-solubility impurity.
By hydrogel dry 24h in vacuum freeze drier of preparation, obtain Graphene-aerosil.
The preparation of d. Graphene-meso-porous titanium dioxide silica aerogel
Graphene-aerosil is placed in Muffle furnace and calcines, is warming up to 540 DEG C (every 10min heats up 15 DEG C), and keeps 6h at 540 DEG C, naturally cool to room temperature.Can template be removed, obtain Graphene-meso-porous titanium dioxide silica aerogel.
Embodiment 3
A. the synthesis of graphite oxide
The reactor of the SPA of the concentrated sulfuric acid and 2.3ml that 20.7ml is housed is placed in ice-water bath, is cooled to 0 DEG C.Add 1g graphite powder, in high degree of agitation, slowly add 3g KMnO
4, maintenance system temperature is no more than 20 DEG C of reaction 1h.Transfer them to 35 ~ 45 DEG C of water-bath 30min.Progressively add 46mL deionized water, temperature rises to 98 DEG C and continues reaction 40min, and mixture becomes glassy yellow by sepia.With the H of 140ml deionized water and mass fraction 30%
2o
2solution-treated, neutralizes unreacted potassium permanganate, with rare HCl cyclic washing filter cake to filtrate without SO
4 2-after, continue to spend deionized water to filtrate weakly acidic pH, be drying to obtain graphite oxide.
B. the preparation of graphene oxide solution
Get 200mg graphite oxide to grind, add 100mL deionized water, after ultrasonic process 30min, the removing of suspension centrifugal treating is a small amount of impurity wherein, obtains the graphene oxide solution of isotropic stable.
C. the preparation of Graphene-aerosil
Get 0.01g NaOH, 0.22g CTAB, 3.7g ethyl orthosilicate, measure the distilled water of 6ml, NaOH, CTAB are dissolved in distilled water, be made into the aqueous solution, then the NaOH aqueous solution, ethyl orthosilicate, graphene oxide solution are slowly added drop-wise to successively in the Keep agitation CTAB aqueous solution, stir 1h, room temperature ageing, after adding reducing agent 0.32g sodium sulfite, be placed in 70 DEG C of reaction 2h, obtain hydrogel.Hydrogel ultra-pure water is replaced 10 times, to remove water-solubility impurity.
By hydrogel dry 24h in vacuum freeze drier of preparation, obtain Graphene-silica dioxide gel aeroge.
The preparation of d. Graphene-meso-porous titanium dioxide silica aerogel
Graphene-silica dioxide gel is placed in Muffle furnace and calcines, is warming up to 540 DEG C (every 10min heats up 15 DEG C), and keeps 6h at 540 DEG C, naturally cool to room temperature.Can template be removed, obtain Graphene-meso-porous titanium dioxide silica aerogel.
Embodiment 4
A. the synthesis of graphite oxide
The reactor of the SPA of the concentrated sulfuric acid and 2.3ml that 20.7ml is housed is placed in ice-water bath, is cooled to 0 DEG C.Add 1g graphite powder, in high degree of agitation, slowly add 3g KMnO
4, maintenance system temperature is no more than 20 DEG C of reaction 1h.Transfer them to 35 ~ 45 DEG C of water-bath 30min.Progressively add 46mL deionized water, temperature rises to 98 DEG C and continues reaction 40min, and mixture becomes glassy yellow by sepia.With the H of 140ml deionized water and mass fraction 30%
2o
2solution-treated, neutralizes unreacted potassium permanganate, with rare HCl cyclic washing filter cake to filtrate without SO
4 2-after, continue to spend deionized water to filtrate weakly acidic pH, be drying to obtain graphite oxide.
B. the preparation of graphene oxide solution
Get 200mg graphite oxide to grind, add 100mL deionized water, after ultrasonic process 30min, the removing of suspension centrifugal treating is a small amount of impurity wherein, obtains the graphene oxide solution of isotropic stable.
C. the preparation of Graphene-silica dioxide gel
Get 0.01g NaOH, 0.22g CTAB, 0.68g NaSiO
39H
2o, measure the distilled water of 6ml, NaOH, CTAB are dissolved in distilled water, are made into the aqueous solution, then by the NaOH aqueous solution, NaSiO
39H
2o, graphene oxide solution are slowly added drop-wise in the Keep agitation CTAB aqueous solution successively, stir 1h, room temperature ageing, after adding reducing agent 0.5g sodium ascorbate, are placed in 70 DEG C of reaction 2h, obtain hydrogel.Hydrogel ultra-pure water is replaced 10 times, to remove water-solubility impurity.
By hydrogel dry 24h in vacuum freeze drier of preparation, obtain Graphene-aerosil.
The preparation of d. Graphene-meso-porous titanium dioxide silica aerogel
Graphene-silica dioxide gel is placed in Muffle furnace and calcines, is warming up to 540 DEG C (every 10min heats up 15 DEG C), and keeps 6h at 540 DEG C, naturally cool to room temperature.Can template be removed, obtain Graphene-meso-porous titanium dioxide silica aerogel.
Fig. 1 is the digital photograph of Graphene in embodiment 1-meso-porous titanium dioxide silica aerogel; Fig. 2 is the XRD figure of Graphene in embodiment 1-meso-porous titanium dioxide silica aerogel; Fig. 3 is the TEM figure of pure graphene aerogel; Fig. 4 is the TEM figure of Graphene in embodiment 1-meso-porous titanium dioxide silica aerogel.Fig. 5 be the aeroge prepared under this experiment condition with the contact angle figure of water droplet, as seen from the figure, the Graphene-meso-porous titanium dioxide silica aerogel of preparation has super-hydrophobicity.
Graphene prepared by the present invention-meso-porous titanium dioxide silica aerogel combines the feature of Graphene, mesoporous silicon oxide and aeroge, is expected in catalyst carrier, adsorbs and be separated, be widely used in high temperature insulating protection etc.
The above, be only the present invention's preferably detailed description of the invention, and just separate method of the present invention and core concept thereof for assistant, this description should not be construed as limitation of the present invention.Protection scope of the present invention is not limited thereto, and is anyly familiar with those skilled in the art in the technical scope that the present invention discloses, and the simple change of the technical scheme that can obtain apparently or equivalence are replaced and all fallen within the scope of protection of the present invention.
Claims (6)
1. a preparation method for Graphene-meso-porous titanium dioxide silica aerogel, is characterized in that, comprise the following steps:
Hummer ' the s method that step 1, employing are improved, is raw material with graphite, prepares graphite oxide: the reactor that the concentrated sulfuric acid and SPA are housed is placed in ice-water bath, the volume ratio 2: 1 ~ 15: 1 of the concentrated sulfuric acid and SPA, be cooled to 0 DEG C, add 1g graphite powder, in high degree of agitation, slowly add 3g KMnO
4, maintenance system temperature is no more than 20 DEG C of reaction 1h, transfers them to 35 ~ 45 DEG C of water-bath 30min, progressively add 46mL deionized water, temperature rises to 98 DEG C and continues reaction 40min, and mixture becomes glassy yellow by sepia, with the H of 140ml deionized water and mass fraction 30%
2o
2solution-treated, neutralizes unreacted potassium permanganate, with rare HCl cyclic washing filter cake to filtrate without SO
4 2-after, continue to spend deionized water to filtrate weakly acidic pH, be drying to obtain graphite oxide;
Step 2, preparation graphene oxide solution: add step 1 and obtain graphite oxide, after carrying out ultrasonic disperse, centrifugation removes unstripped graphite oxide and impurity, until form the uniform graphene oxide solution of sepia; The graphene oxide solution stable existence obtained at least 1 ~ 24 hours;
The preparation of step 3, Graphene-aerosil: the graphene oxide water solution that the NaOH aqueous solution, silicon source and step 2 are obtained, slowly be added drop-wise to successively in the softex kw aqueous solution of Keep agitation, the mol ratio of reactant is 0.12CTAB: 1 silicon source: 0.6NaOH: 100H
2o: χ graphene oxide, reaction 1 ~ 12h, room temperature ageing, after adding reducing agent, be placed in 70 ~ 100 DEG C of baking oven reaction 1 ~ 10h, obtain hydrogel, the product obtained is washed,-70 ~-90 DEG C of drying 12 ~ 24h in vacuum freeze drier, are not removed the Graphene-aerosil of template;
The preparation of step 4, Graphene-meso-porous titanium dioxide silica aerogel: template softex kw removed by aeroge step 3 obtained, and obtains Graphene-meso-porous titanium dioxide silica aerogel.
2. the preparation method of Graphene according to claim 1-meso-porous titanium dioxide silica aerogel, is characterized in that, the supersonic frequency of ultrasonic disperse described in step 2 is 20 ~ 60KHz; The rotating speed of described centrifugation is 1000 ~ 6000 revs/min.
3. the preparation method of Graphene according to claim 1-meso-porous titanium dioxide silica aerogel, it is characterized in that, the mass ratio in graphene oxide and silicon source described in preferred step 3 is 1: 8 ~ 1: 40, wherein, described silicon source is selected from: ethyl orthosilicate, sodium metasilicate, natural montmorillonite, saponite.
4. the preparation method of Graphene according to claim 1-meso-porous titanium dioxide silica aerogel, is characterized in that, the mass ratio of reducing agent described in step 3 and graphene oxide is 5: 1 ~ 200: 1.Wherein, described reducing agent is selected from: ascorbic acid, sodium ascorbate, sodium sulfite, sodium thiosulfate.
5. the preparation method of Graphene according to claim 1-meso-porous titanium dioxide silica aerogel, it is characterized in that, the method removing template described in step 4 is roasting method, aeroge is placed in Muffle furnace and calcines, be warming up to 400 ~ 700 DEG C, every 10min heats up 15 DEG C, and keeps 1 ~ 6h at such a temperature, naturally cools to room temperature.
6. the preparation method of Graphene according to claim 1-meso-porous titanium dioxide silica aerogel, is characterized in that, the method removing template described in step 4 is solvent extraction, after step 3 obtains Graphene-silica hydrogel, with EtOH/CH
3cOONa is extractant, removes softex kw; Washed by the hydrogel removing template, in vacuum freeze drier ,-70 ~-90 DEG C of drying 12 ~ 24h, obtain aeroge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510161956.4A CN104826582B (en) | 2015-04-04 | 2015-04-04 | A kind of preparation method of graphene meso-porous titanium dioxide silica aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510161956.4A CN104826582B (en) | 2015-04-04 | 2015-04-04 | A kind of preparation method of graphene meso-porous titanium dioxide silica aerogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104826582A true CN104826582A (en) | 2015-08-12 |
| CN104826582B CN104826582B (en) | 2017-09-29 |
Family
ID=53804993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510161956.4A Active CN104826582B (en) | 2015-04-04 | 2015-04-04 | A kind of preparation method of graphene meso-porous titanium dioxide silica aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104826582B (en) |
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457597A (en) * | 2015-12-08 | 2016-04-06 | 华南理工大学 | Graphene/silicon dioxide/nano zero-valent iron composite as well as preparation method and application thereof |
| CN105521770A (en) * | 2016-01-21 | 2016-04-27 | 青岛大学 | Preparation method of graphene oxide and polyvinyl alcohol hybrid aerogel |
| CN105752966A (en) * | 2016-01-27 | 2016-07-13 | 同济大学 | Preparation method of graphene/hollow carbon nanometer balls |
| CN106711459A (en) * | 2016-11-22 | 2017-05-24 | 成都新柯力化工科技有限公司 | Aerogel-networked lithium battery anode additive and preparation method |
| CN106910640A (en) * | 2017-04-17 | 2017-06-30 | 上海应用技术大学 | Controllable graphene nanometer sheet electrode material of a kind of form and its preparation method and application |
| CN107159107A (en) * | 2016-03-08 | 2017-09-15 | 常州烃环保科技有限公司 | A kind of preparation method of graphene/silicon aeroge compound adsorbent |
| CN107216115A (en) * | 2017-06-26 | 2017-09-29 | 南京工业大学 | A kind of PTFE fiber cloth composite graphite alkene SiO2The preparation method of aeroge |
| CN107226923A (en) * | 2017-06-12 | 2017-10-03 | 安徽省颍上县正泰电器有限责任公司 | A kind of preparation method of modified graphene and nano-cellulose compound temperature-sensitive material |
| CN107235744A (en) * | 2017-06-02 | 2017-10-10 | 东南大学 | A kind of preparation method of graphene aerosil |
| CN107325328A (en) * | 2017-06-15 | 2017-11-07 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide compound particle |
| CN107433171A (en) * | 2017-06-12 | 2017-12-05 | 安徽省颍上县正泰电器有限责任公司 | A kind of preparation method of the mesoporous carbon nano tube composite fibre nanometer titanium dioxide Silica hydrogel of temperature sensitive type |
| CN108083262A (en) * | 2018-02-01 | 2018-05-29 | 济南大学 | A kind of preparation method of redox graphene-silica block aeroge |
| CN108176377A (en) * | 2018-01-23 | 2018-06-19 | 贵州省建材产品质量监督检验院 | The preparation method of open celled foam/graphite oxide aerogel composite adsorbing material |
| CN108218386A (en) * | 2018-01-23 | 2018-06-29 | 贵州省建材产品质量监督检验院 | Chlorosilane modified graphene oxide/silica heat-preserving complex material preparation method |
| CN108325507A (en) * | 2018-03-30 | 2018-07-27 | 江苏大学 | A kind of mesoporous silicon fiml of graphene oxide doped and its preparation method and application |
| CN108706684A (en) * | 2018-07-17 | 2018-10-26 | 东莞市武华新材料有限公司 | A kind of oil water separator system for the sewage disposal containing organic matter |
| CN108728107A (en) * | 2018-05-25 | 2018-11-02 | 合肥慧谷农业科技有限公司 | A kind of soil conditioner and preparation method thereof handling heavy metal |
| CN108807835A (en) * | 2017-04-28 | 2018-11-13 | 福建新峰二维材料科技有限公司 | The preparation method and battery of one type of metal graphene negative material |
| CN108905981A (en) * | 2018-07-12 | 2018-11-30 | 山东联星能源集团有限公司 | A kind of graphene/CNTs aeroge preparation method of low cost absorption heavy metal ion |
| CN109225130A (en) * | 2018-07-16 | 2019-01-18 | 江汉大学 | A kind of preparation method of three-dimensional magnetic graphene composite material |
| CN109319796A (en) * | 2018-09-28 | 2019-02-12 | 东北大学秦皇岛分校 | A kind of aerosil and preparation method thereof |
| CN109867277A (en) * | 2017-12-04 | 2019-06-11 | 武汉大学 | A kind of preparation method of big size graphene three-dimensional material |
| CN110152569A (en) * | 2018-04-28 | 2019-08-23 | 浙江大学 | A kind of nanometer Fe O (OH) composite aerogel, preparation method and use |
| CN110304879A (en) * | 2019-06-28 | 2019-10-08 | 济南大学 | A kind of method making concrete with water body purification function and the concrete with water body purification function |
| CN110394150A (en) * | 2019-07-17 | 2019-11-01 | 江苏大学 | A kind of meso-porous titanium dioxide silica aerogel and its preparation method and application that lanthanum is modified |
| CN110420623A (en) * | 2019-08-05 | 2019-11-08 | 山西工程技术学院 | A kind of compound porous adsorbent material of vermiculite base graphene and preparation method thereof |
| CN110523375A (en) * | 2019-08-15 | 2019-12-03 | 江苏大学 | A kind of preparation method and application for the big mesoporous film of redox graphene/silica that lanthanum is modified |
| CN110743379A (en) * | 2019-11-07 | 2020-02-04 | 北京航空航天大学 | Application of mesoporous silica nanosheet composite film in water treatment |
| CN110860280A (en) * | 2019-12-31 | 2020-03-06 | 新兴远建（天津）新材料科技有限公司 | Composite hybrid hydrogel with high adsorption capacity and preparation method and application thereof |
| CN111215029A (en) * | 2020-01-21 | 2020-06-02 | 中国科学院上海硅酸盐研究所 | Graphene sponge capable of being directly baked at high temperature and reused, and preparation method and application thereof |
| CN111320970A (en) * | 2018-12-13 | 2020-06-23 | 山东欧铂新材料有限公司 | Nano-silica composite graphene cooling liquid and preparation method thereof |
| CN112934211A (en) * | 2021-01-29 | 2021-06-11 | 广西交科集团有限公司 | Preparation method of silica aerogel with photocatalytic activity |
| CN114105123A (en) * | 2020-08-27 | 2022-03-01 | 中国科学院大连化学物理研究所 | Elastic graphene-based composite sizing phase-change material and preparation and application thereof |
| CN114775298A (en) * | 2022-03-11 | 2022-07-22 | 广东机电职业技术学院 | Composite material containing graphene aerogel and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456569A (en) * | 2008-07-22 | 2009-06-17 | 绍兴纳诺气凝胶新材料研发中心有限公司 | Method for quick-speed preparing aerogel by hydro-thermal synthesis at low cost |
| CN102909005A (en) * | 2012-10-24 | 2013-02-06 | 中国科学院理化技术研究所 | Graphene-based composite material with surface coated by mesoporous silica and loaded with noble metal nanoparticles, as well as preparation method and application of graphene-based composite material |
| CN104098089A (en) * | 2014-07-25 | 2014-10-15 | 西南民族大学 | Preparation method for doped graphene foams |
| CN104134805A (en) * | 2014-07-29 | 2014-11-05 | 武汉理工大学 | Flexible three-dimensional nano bioelectrode and preparation method thereof |
| CN104326484A (en) * | 2014-10-12 | 2015-02-04 | 吉林大学 | Molecular-sieve nanotube aerogel and preparation method thereof |
-
2015
- 2015-04-04 CN CN201510161956.4A patent/CN104826582B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456569A (en) * | 2008-07-22 | 2009-06-17 | 绍兴纳诺气凝胶新材料研发中心有限公司 | Method for quick-speed preparing aerogel by hydro-thermal synthesis at low cost |
| CN102909005A (en) * | 2012-10-24 | 2013-02-06 | 中国科学院理化技术研究所 | Graphene-based composite material with surface coated by mesoporous silica and loaded with noble metal nanoparticles, as well as preparation method and application of graphene-based composite material |
| CN104098089A (en) * | 2014-07-25 | 2014-10-15 | 西南民族大学 | Preparation method for doped graphene foams |
| CN104134805A (en) * | 2014-07-29 | 2014-11-05 | 武汉理工大学 | Flexible three-dimensional nano bioelectrode and preparation method thereof |
| CN104326484A (en) * | 2014-10-12 | 2015-02-04 | 吉林大学 | Molecular-sieve nanotube aerogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 罗玲玲: "石墨烯基复合介孔材料的制备及其对亚甲基蓝的吸附性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457597A (en) * | 2015-12-08 | 2016-04-06 | 华南理工大学 | Graphene/silicon dioxide/nano zero-valent iron composite as well as preparation method and application thereof |
| CN105457597B (en) * | 2015-12-08 | 2018-02-27 | 华南理工大学 | A kind of graphene/silicon dioxide/nano zero-valence iron composite material and preparation method and application |
| CN105521770A (en) * | 2016-01-21 | 2016-04-27 | 青岛大学 | Preparation method of graphene oxide and polyvinyl alcohol hybrid aerogel |
| CN105752966B (en) * | 2016-01-27 | 2017-12-15 | 同济大学 | A kind of preparation method of graphene/hollow Nano carbon balls |
| CN105752966A (en) * | 2016-01-27 | 2016-07-13 | 同济大学 | Preparation method of graphene/hollow carbon nanometer balls |
| CN107159107A (en) * | 2016-03-08 | 2017-09-15 | 常州烃环保科技有限公司 | A kind of preparation method of graphene/silicon aeroge compound adsorbent |
| CN106711459A (en) * | 2016-11-22 | 2017-05-24 | 成都新柯力化工科技有限公司 | Aerogel-networked lithium battery anode additive and preparation method |
| CN106711459B (en) * | 2016-11-22 | 2019-07-19 | 上海太洋科技有限公司 | A kind of cathode of lithium battery additive and preparation method containing aeroge network |
| CN106910640A (en) * | 2017-04-17 | 2017-06-30 | 上海应用技术大学 | Controllable graphene nanometer sheet electrode material of a kind of form and its preparation method and application |
| CN108807835A (en) * | 2017-04-28 | 2018-11-13 | 福建新峰二维材料科技有限公司 | The preparation method and battery of one type of metal graphene negative material |
| CN107235744A (en) * | 2017-06-02 | 2017-10-10 | 东南大学 | A kind of preparation method of graphene aerosil |
| CN107433171A (en) * | 2017-06-12 | 2017-12-05 | 安徽省颍上县正泰电器有限责任公司 | A kind of preparation method of the mesoporous carbon nano tube composite fibre nanometer titanium dioxide Silica hydrogel of temperature sensitive type |
| CN107226923A (en) * | 2017-06-12 | 2017-10-03 | 安徽省颍上县正泰电器有限责任公司 | A kind of preparation method of modified graphene and nano-cellulose compound temperature-sensitive material |
| CN107325328A (en) * | 2017-06-15 | 2017-11-07 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide compound particle |
| CN107325328B (en) * | 2017-06-15 | 2019-06-07 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide compound particle |
| CN107216115B (en) * | 2017-06-26 | 2019-10-29 | 南京工业大学 | A kind of preparation method of PTFE fiber cloth composite graphite alkene-SiO2 aeroge |
| CN107216115A (en) * | 2017-06-26 | 2017-09-29 | 南京工业大学 | A kind of PTFE fiber cloth composite graphite alkene SiO2The preparation method of aeroge |
| CN109867277A (en) * | 2017-12-04 | 2019-06-11 | 武汉大学 | A kind of preparation method of big size graphene three-dimensional material |
| CN108176377A (en) * | 2018-01-23 | 2018-06-19 | 贵州省建材产品质量监督检验院 | The preparation method of open celled foam/graphite oxide aerogel composite adsorbing material |
| CN108218386A (en) * | 2018-01-23 | 2018-06-29 | 贵州省建材产品质量监督检验院 | Chlorosilane modified graphene oxide/silica heat-preserving complex material preparation method |
| CN108218386B (en) * | 2018-01-23 | 2021-01-08 | 贵州省建材产品质量监督检验院 | Preparation method of chlorosilane modified graphene oxide/silicon dioxide heat-insulation composite material |
| CN108083262A (en) * | 2018-02-01 | 2018-05-29 | 济南大学 | A kind of preparation method of redox graphene-silica block aeroge |
| CN108083262B (en) * | 2018-02-01 | 2021-03-19 | 济南大学 | Preparation method of reduced graphene oxide-silicon dioxide block aerogel |
| CN108325507A (en) * | 2018-03-30 | 2018-07-27 | 江苏大学 | A kind of mesoporous silicon fiml of graphene oxide doped and its preparation method and application |
| CN110152569A (en) * | 2018-04-28 | 2019-08-23 | 浙江大学 | A kind of nanometer Fe O (OH) composite aerogel, preparation method and use |
| CN110152569B (en) * | 2018-04-28 | 2022-07-08 | 浙江大学 | Nano FeO (OH) composite aerogel, preparation method and application thereof |
| CN108728107A (en) * | 2018-05-25 | 2018-11-02 | 合肥慧谷农业科技有限公司 | A kind of soil conditioner and preparation method thereof handling heavy metal |
| CN108905981A (en) * | 2018-07-12 | 2018-11-30 | 山东联星能源集团有限公司 | A kind of graphene/CNTs aeroge preparation method of low cost absorption heavy metal ion |
| CN109225130A (en) * | 2018-07-16 | 2019-01-18 | 江汉大学 | A kind of preparation method of three-dimensional magnetic graphene composite material |
| CN109225130B (en) * | 2018-07-16 | 2022-05-03 | 江汉大学 | Application of three-dimensional magnetic graphene composite material in adsorption of perfluorinated compounds |
| CN108706684A (en) * | 2018-07-17 | 2018-10-26 | 东莞市武华新材料有限公司 | A kind of oil water separator system for the sewage disposal containing organic matter |
| CN109319796A (en) * | 2018-09-28 | 2019-02-12 | 东北大学秦皇岛分校 | A kind of aerosil and preparation method thereof |
| CN111320970A (en) * | 2018-12-13 | 2020-06-23 | 山东欧铂新材料有限公司 | Nano-silica composite graphene cooling liquid and preparation method thereof |
| CN110304879A (en) * | 2019-06-28 | 2019-10-08 | 济南大学 | A kind of method making concrete with water body purification function and the concrete with water body purification function |
| CN110394150A (en) * | 2019-07-17 | 2019-11-01 | 江苏大学 | A kind of meso-porous titanium dioxide silica aerogel and its preparation method and application that lanthanum is modified |
| CN110394150B (en) * | 2019-07-17 | 2022-05-20 | 江苏大学 | Lanthanum-modified mesoporous silica aerogel and preparation method and application thereof |
| CN110420623B (en) * | 2019-08-05 | 2022-05-17 | 山西工程技术学院 | Vermiculite-based graphene composite porous adsorption material and preparation method thereof |
| CN110420623A (en) * | 2019-08-05 | 2019-11-08 | 山西工程技术学院 | A kind of compound porous adsorbent material of vermiculite base graphene and preparation method thereof |
| CN110523375A (en) * | 2019-08-15 | 2019-12-03 | 江苏大学 | A kind of preparation method and application for the big mesoporous film of redox graphene/silica that lanthanum is modified |
| CN110743379A (en) * | 2019-11-07 | 2020-02-04 | 北京航空航天大学 | Application of mesoporous silica nanosheet composite film in water treatment |
| CN110743379B (en) * | 2019-11-07 | 2023-11-14 | 北京航空航天大学 | Application of mesoporous silica nano-sheet composite film in water treatment |
| CN110860280A (en) * | 2019-12-31 | 2020-03-06 | 新兴远建（天津）新材料科技有限公司 | Composite hybrid hydrogel with high adsorption capacity and preparation method and application thereof |
| CN111215029A (en) * | 2020-01-21 | 2020-06-02 | 中国科学院上海硅酸盐研究所 | Graphene sponge capable of being directly baked at high temperature and reused, and preparation method and application thereof |
| CN114105123A (en) * | 2020-08-27 | 2022-03-01 | 中国科学院大连化学物理研究所 | Elastic graphene-based composite sizing phase-change material and preparation and application thereof |
| CN112934211A (en) * | 2021-01-29 | 2021-06-11 | 广西交科集团有限公司 | Preparation method of silica aerogel with photocatalytic activity |
| CN114775298A (en) * | 2022-03-11 | 2022-07-22 | 广东机电职业技术学院 | Composite material containing graphene aerogel and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104826582B (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104826582A (en) | Preparation method of graphene-mesoporous silica aerogel | |
| Wu et al. | Effects of poly (vinyl alcohol)(PVA) content on preparation of novel thiol-functionalized mesoporous PVA/SiO2 composite nanofiber membranes and their application for adsorption of heavy metal ions from aqueous solution | |
| US10618813B2 (en) | Carbon nitride modified with perylenetetracarboxylic dianhydride / graphene oxide aerogel composite material, preparation method and application thereof | |
| CN102179230B (en) | Preparation method of magnetized silicon dioxide aerogel | |
| CN109772418A (en) | P-doped tubulose carbonitride micro Nano material and its application in exhaust fume catalytic processing | |
| CN103480333A (en) | Compound grapheme absorption agent, method for preparing compound grapheme absorption agent and application of compound grapheme absorption agent | |
| CN105457597B (en) | A kind of graphene/silicon dioxide/nano zero-valence iron composite material and preparation method and application | |
| CN102616778A (en) | Method for preparing mesoporous activated carbon by regenerating waste coal-based activated carbon through microwave heating | |
| CN107837816B (en) | Fe2O3/g-C3N4Composite system, preparation method and application | |
| CN111889066B (en) | PH response controlled release hollow mesoporous silica nanoparticle and preparation method thereof | |
| CN108499525B (en) | Preparation method of adsorbent for purifying hydrogen peroxide solution and purification method of hydrogen peroxide | |
| CN109081350A (en) | A kind of method that watery fusion salt medium prepares nano-silicon | |
| CN103706328A (en) | Nitrogen hybridized magnetic ordered mesoporous carbon adsorbent, and preparation method and application thereof | |
| CN105032375A (en) | Preparation method of magnetic graphite-based heavy metal adsorbing material | |
| Si et al. | Simultaneous removal of nitrogen and phosphorus by magnesium-modified calcium silicate core-shell material in water | |
| CN113000023A (en) | Graphene oxide modified activated carbon, preparation method thereof and water treatment method | |
| CN104623973B (en) | A kind of Modified Quartz Sand and method of modifying thereof | |
| CN108201876B (en) | Method for deeply adsorbing zinc ions by using NaP molecular sieve | |
| CN108404850A (en) | A kind of mesoporous manganese oxide adsorbent and the method for preparing adsorbent using corona treatment | |
| Li et al. | Synthesis of UiO-66 series metal–organic framework composites and the adsorption effect on gallium | |
| CN106902758A (en) | A kind of preparation and application of the Graphene adsorbent of aerobic particle mud N doping | |
| CN117339551A (en) | Composite material synthesis method with reduction and adsorption effects on tellurium | |
| CN105460963B (en) | Preparation method of nanometer mesoporous alumina | |
| CN114377647B (en) | Preparation method and application of modified attapulgite-loaded ferrous sulfide | |
| CN116459785A (en) | Preparation method of halloysite nanotube composite material and application of halloysite nanotube composite material in uranium pollution treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |