CN104785235A - Preparation method for modified graphene-loaded titanium dioxide composite photocatalyst - Google Patents
Preparation method for modified graphene-loaded titanium dioxide composite photocatalyst Download PDFInfo
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- CN104785235A CN104785235A CN201510133238.6A CN201510133238A CN104785235A CN 104785235 A CN104785235 A CN 104785235A CN 201510133238 A CN201510133238 A CN 201510133238A CN 104785235 A CN104785235 A CN 104785235A
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Abstract
The invention discloses a preparation method for a modified graphene-loaded titanium dioxide composite photocatalyst. The method comprises the following steps: obtaining a graphene oxide suspension through an improved Hummers method, and adding triethanolamine into the graphene oxide suspension for reacting to obtain a modified graphene oxide suspension liquid; dropwise adding the obtained modified graphene oxide suspension liquid into a sulfuric acid solution in which titanyl sulfate is dissolved; performing ultrasonic auxiliary soaking, and then performing centrifugal separation to obtain a composite photocatalyst precursor; adding the composite photocatalyst precursor into an alkali solution to perform hydrothermal reaction; pre-drying a hydrothermal reaction product, and performing high-temperature calcining and reducing in an air atmosphere to obtain the modified graphene-loaded titanium dioxide composite photocatalyst which is stable in structure, high in specific surface area, high in photocatalytic activity, small in titanium dioxide particle size (about 10 nm), uniform in distribution, and difficult to agglomerate. The method is easy to operate and low in cost, and meets industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of modified graphene carried titanium dioxide composite photo-catalyst, belong to photocatalyst technology field.
Background technology
Titanium dioxide semiconductor has that oxidability is strong, the advantage such as complete and reusable of degrading, and has huge using value in photocatalysis field.And how prepared by simple technique that particle diameter is little, the high-performance titanium deoxide catalyst of good dispersion is one of hot issue of current photocatalysis research field.As a kind of New Two Dimensional structural carbon material, Graphene has excellent electricity, calorifics and mechanical property, is extensively studied in fields such as electronics, sensing, catalysis, biomedicines.With graphene film, to be carrier loaded titanium dioxide be when the research direction of previous hot topic, this is because the theoretical specific surface area that Graphene has superelevation (is about 2630m
2/ g) and electronic conduction ability (be about 2 × 10
5cm
2v
-1s
-1), enough reaction site can not only be provided for optically catalytic TiO 2, and effectively can reduce the recombination rate of electron-hole pair, thus significantly improve the photocatalytic activity of titanium dioxide.But the low pole of carbon atom makes with the interaction of other medium more weak in graphene layer, and between carbon-coating, Van der Waals force causes easy reunion, makes its more difficult dispersion in the common solvents such as aqueous phase.In order to give full play to the excellent properties of Graphene, improving its molding processibility (as increased solubility, improve dispersed etc. in the base), needing to carry out modification to it.It is that reducing agent is prepared Graphene, under the repair of alcohol vapour, then prepared the technology path of modified graphene that Chinese patent 201210428350.9 discloses with hydroiodic acid, the method improves the defect of graphenic surface to a certain extent, for improving the conductance of Graphene.
Summary of the invention
For the technological deficiency preparing the existence of graphene-supported composite titania material in prior art, the object of the present invention is to provide a kind of Stability Analysis of Structures, there is high specific surface area and highlight catalytic active and titanium dioxide particle diameter is little, the preparation method of modified graphene carried titanium dioxide composite photo-catalyst that is evenly distributed, not easily reunites, the method is simple to operate, cost is low, meets suitability for industrialized production.
The invention provides a kind of preparation method of modified graphene carried titanium dioxide composite photo-catalyst, the method first obtains graphene oxide suspension by the Hummers method improved, in graphene oxide suspension, add triethanolamine react at 60 ~ 120 DEG C of temperature, obtain modified graphene oxide suspension; Being added to by gained modified graphene oxide hanging drop is dissolved with in the sulfuric acid solution of titanyl sulfate, and after ultrasonic assistant soakage, centrifugation, obtains composite photo-catalyst presoma; Gained composite photo-catalyst presoma joins in alkaline solution, hydro-thermal reaction is carried out at 70 ~ 100 DEG C of temperature, hydro-thermal reaction product after predrying, at 400 ~ 500 DEG C of temperature in air atmosphere calcining reduction, obtain modified graphene carried titanium dioxide composite photo-catalyst.
The present invention also comprises following preferred version about the preparation method of modified graphene carried titanium dioxide composite photo-catalyst:
The graphene oxide suspension concentration obtained by the Hummers method improved in preferred version is 1 ~ 20mg/mL, more preferably 1 ~ 10mg/mL.
In preferred version, in triethanolamine and graphene oxide suspension, the mass ratio of graphene oxide is 1:1 ~ 10:1, more preferably 1:1 ~ 5:1.
The time that in preferred version, graphene oxide and triethanolamine react at 60 ~ 120 DEG C of temperature is 1 ~ 5h, more preferably 1 ~ 3h.Under the temperature conditions of technical solution of the present invention, the suitable time can make triethanolamine and graphene oxide fully react, and surface of graphene oxide evenly modifies a large amount of hydroxyls, carboxyl, quaternary amines etc.
In preferred version, in sulfuric acid solution, the concentration of sulfuric acid is 0.1 ~ 1mol/L, more preferably 0.1 ~ 0.5mol/L.
In preferred version, the time of ultrasonic assistant soakage is 0.5 ~ 4h, more preferably 1 ~ 3h.Suitable dip time, can make the oxygen titanium cation be dissolved with in the sulfuric acid solution of titanyl sulfate fully be adsorbed onto on the hydroxyl on modified graphene oxide surface, carboxyl, quaternary amines.
Preferred version neutral and alkali solution is Na
2cO
3solution, K
2cO
3at least one in solution, NaOH solution, KOH solution.
Preferred version neutral and alkali solution concentration is 0.1 ~ 1mol/L, more preferably 0.1 ~ 0.5mol/L.
In preferred version, the hydro-thermal reaction time is 15 ~ 30h, more preferably 15 ~ 25h.
In preferred version, the calcining reduction time is 1 ~ 5h, more preferably 1 ~ 4h.
In preferred version in modified graphene carried titanium dioxide composite photo-catalyst the mass percentage of Graphene between 1 ~ 25%.
In the ratio of 1 ~ 10g/100 ~ 500mL, titanyl sulfate vitriolization solution is obtained the sulfuric acid solution containing aerobic titanium cation in preferred version.
First passage triethanolamine of the present invention carries out surface modification to graphene oxide, surface of graphene oxide is made to be uniformly distributed great amount of hydroxy group, carboxyl and quaternary amines, on this basis with the oxygen titanium cation that these groups absorption titanyl sulfate produces in sulfuric acid solution, make the dispersed absorption carriage of oxygen titanium cation in surface of graphene oxide, eventually pass hydro-thermal reaction and high-temperature calcination is reduced, obtain structural stability, there is high specific surface area and photocatalytic activity, and titanium dioxide particle diameter is little, be evenly distributed, the modified graphene carried titanium dioxide composite photo-catalyst of not easily reuniting.
Hinge structure, the Advantageous Effects that the present invention brings is:
(1) adopt Graphene as catalyst carrier, its lamellar structure destructiveness is less, is conducive to the separation of electron-hole pair.
(2) by triethanolamine modified graphene oxide surface, its surface uniform is made to modify great amount of hydroxy group, carboxyl, quaternary amines, can Electrostatic Absorption oxygen titanium cation, ensure that the load capacity of titanium dioxide, and the titanium dioxide particle diameter generated is little, dispersed does not reunite.
(3) adopt constitutionally stable Graphene as catalyst carrier, while enhancing electron transmission effect, raising photocatalysis efficiency, effectively can also avoid the catalysqt deactivation phenomenon caused due to catalyst carrier damage, thus the service life of extending catalyst.
(4) preparation method's technique is simple, cost is low, meet suitability for industrialized production.
(5) the modified graphene carried titanium dioxide composite photo-catalyst prepared demonstrates huge application potential in photocatalysis field.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of modified graphene carried titanium dioxide composite photo-catalyst prepared by the embodiment of the present invention 1;
Fig. 2 is the high power transmission electron microscope picture of modified graphene carried titanium dioxide composite photo-catalyst prepared by the embodiment of the present invention 1;
Fig. 3 is the transmission electron microscope picture of the graphene-supported titanium dioxide composite photocatalyst of comparative example 1 gained;
Fig. 4 is the transmission electron microscope picture of comparative example 2 gained titanium dioxide optical catalyst;
Fig. 5 is the photocatalysis performance curve map of the obtained composite catalyst of embodiment 1 ~ 3 and comparative example 1 and 2 and catalyst, and wherein curve M B is the degradation curve of methylene blue when not adding photochemical catalyst, and in figure, G represents Graphene.
Detailed description of the invention
Following examples are intended to further illustrate content of the present invention, instead of the protection domain of restriction the claims in the present invention.
The graphene oxide used in following examples and comparative example 1 is all standby by the Hummers legal system improved, the Hummers legal system improved is conventional maturation method for graphene oxide, all meets enforcement technical scheme of the present invention according to the graphene oxide that the Hummers legal system of existing improvement is standby.
Hummers legal system by improving in the present invention for the detailed process of graphene oxide is: be add 1g potassium peroxydisulfate and 1g phosphorus pentoxide in the concentrated sulfuric acid of 98% toward 20mL mass concentration, be heated with stirring to 80 DEG C, after potassium peroxydisulfate and phosphorus pentoxide fully dissolve, add 2g graphite, continue to heat 4.5h with this understanding.The washing of cooled and filtered, distilled water, to neutral, obtains pre-oxidation graphite after natural drying in air.Pre-oxidation graphite is added in the 75mL concentrated sulfuric acid, under ice bath, slowly adds 10g potassium permanganate, control this process temperature and be no more than 20 DEG C.35 DEG C are warming up to after having added, ice bath is transferred to after reaction 2h, slowly add 160mL distilled water, in the process that adds water, control temperature is lower than 50 DEG C, 500mL distilled water is added again after reaction 2h, dropwise add the aqueous hydrogen peroxide solution that 8.3mL mass concentration is 30%, continue to stir 30min, then leave standstill 8h.Outwell supernatant liquor, adding 800mL concentration is 10% hydrochloric acid solution, stirs 3h and leaves standstill 8h.Again outwell supernatant liquor, add 400mL distilled water, stir 3h.Gained mixed liquor is centrifugal 1h under 5000rpm, outwell clear liquid, remaining part adds the centrifugal 1h of distilled water again, repeatedly wash to pH be neutral (number of repetition is about 12 times), add water and regulate graphene oxide suspension concentration to be 5.5mg/mL, save backup.Graphene oxide in following examples all adopts the method to prepare.
Embodiment 1
Be add 6mL triethanolamine in the graphene oxide suspension of 5.5mg/mL, stirring reaction 2h at 80 DEG C toward 400mL concentration.Centrifuge washing in neutral, obtains the graphene oxide suspension through triethanolamine modification to eluent.10g titanyl sulfate being dissolved in 500mL concentration is in the sulfuric acid solution of 0.3mol/L, obtain oxygen titanium cation solution, 240mL is added drop-wise in above-mentioned oxygen titanium cation solution through the graphene oxide suspension of triethanolamine modification, centrifugation after ultrasonic assistant soakage 2h, obtains solid-state catalyst precursor.Be the Na of 0.1mol/L by 70mL concentration
2cO
3solution is transferred in teflon-lined water heating kettle after being disperseed by catalyst precursor, is placed in 80 DEG C of baking oven hydro-thermal reaction 20h.By reactant mixture centrifuge washing to neutral, proceed to 450 DEG C of calcining reduction 2h in Muffle furnace after the 80 DEG C of dryings of gained solid, obtain new modified graphene-supported titanium dioxide composite photocatalyst.Identified as samples is designated as f-G/T (1).
Embodiment 2
Be add 5mL triethanolamine in the graphene oxide suspension of 5.5mg/mL, stirring reaction 2h at 120 DEG C toward 400mL concentration.Centrifuge washing in neutral, obtains the graphene oxide suspension through triethanolamine modification to eluent.10g titanyl sulfate being dissolved in 500mL concentration is in the sulfuric acid solution of 0.5mol/L, obtain oxygen titanium cation solution, 240mL is added drop-wise in above-mentioned oxygen titanium cation solution through the graphene oxide suspension of triethanolamine modification, centrifugation after ultrasonic assistant soakage 3h, obtains solid-state catalyst precursor.Be the Na of 0.3mol/L by 70mL concentration
2cO
3solution is transferred in teflon-lined water heating kettle after being disperseed by catalyst precursor, is placed in 70 DEG C of baking oven hydro-thermal reaction 25h.By reactant mixture centrifuge washing to neutral, proceed to 500 DEG C of calcining reduction 1h in Muffle furnace after the 80 DEG C of dryings of gained solid, obtain new modified graphene-supported titanium dioxide composite photocatalyst.Identified as samples is designated as f-G/T (2).
Embodiment 3
Be add 3mL triethanolamine in the graphene oxide suspension of 5.5mg/mL, stirring reaction 3h at 60 DEG C toward 400mL concentration.Centrifuge washing in neutral, obtains the graphene oxide suspension through triethanolamine modification to eluent.10g titanyl sulfate being dissolved in 500mL concentration is in the sulfuric acid solution of 0.1mol/L, obtain oxygen titanium cation solution, 240mL is added drop-wise in above-mentioned oxygen titanium cation solution through the graphene oxide suspension of triethanolamine modification, centrifugation after ultrasonic assistant soakage 1h, obtains solid-state catalyst precursor.Be the Na of 0.5mol/L by 70mL concentration
2cO
3solution is transferred in teflon-lined water heating kettle after being disperseed by catalyst precursor, is placed in 100 DEG C of baking oven hydro-thermal reaction 15h.By reactant mixture centrifuge washing to neutral, proceed to 400 DEG C of calcining reduction 4h in Muffle furnace after the 80 DEG C of dryings of gained solid, obtain new modified graphene-supported titanium dioxide composite photocatalyst.Identified as samples is designated as f-G/T (3).
Comparative example 1
10g titanyl sulfate being dissolved in 500mL concentration is in the sulfuric acid solution of 0.3mol/L, obtain oxygen titanium cation solution, be that the graphene oxide suspension of 5.5mg/mL is added drop-wise in above-mentioned oxygen titanium cation solution by 240mL concentration, centrifugation after ultrasonic assistant soakage 2h, obtains solid-state catalyst precursor.Be the Na of 0.1mol/L by 70mL concentration
2cO
3solution is transferred in teflon-lined water heating kettle after being disperseed by catalyst precursor, is placed in 80 DEG C of baking oven hydro-thermal reaction 20h.By reactant mixture centrifuge washing to neutral, proceed to 450 DEG C of calcining reduction 2h in Muffle furnace after the 80 DEG C of dryings of gained solid, obtain graphene-supported titanium dioxide composite photocatalyst.Identified as samples is designated as G/T.
Comparative example 2
10g titanyl sulfate being dissolved in 500mL concentration is in the sulfuric acid solution of 0.3mol/L, obtains oxygen titanium cation solution, toward wherein adding the Na that 70mL concentration is 0.1mol/L
2cO
3solution, stirring mixing.Get 70mL gained mixed liquor and transfer in teflon-lined water heating kettle, being placed in 80 DEG C of baking oven hydro-thermal reaction 20h.By reactant mixture centrifuge washing to neutral, proceed to 450 DEG C of calcining 2h in Muffle furnace after the 80 DEG C of dryings of gained solid, obtain titanium dioxide optical catalyst.Identified as samples is designated as TiO
2.
Embodiment 4
The sign of modified graphene carried titanium dioxide composite photo-catalyst prepared by embodiment 1 ~ 3 and comparative example 1 and 2 and titanium dioxide optical catalyst and performance test.
Microscopic appearance is observed: with U.S. Tecnai G
220ST type transmission electron microscope carries out microscopic appearance observation to gained photochemical catalyst.
Photocatalysis performance is tested: get 0.1g photochemical catalyst sample and join in methylene blue (MB) aqueous solution that 100mL concentration is 10mg/L.After lucifuge ultrasonic disperse, under dark condition, stir 30min, make it reach absorption-desorption balance.Light source distance solution surface 20cm in photocatalytic degradation device, obtains supernatant every take a morsel degradation solution, centrifugal 5min of 20min, measures the absorbance of supernatant Methylene Blue with 752N type ultraviolet-uisible spectrophotometer.Obtain corresponding concentration according to calibration curve, calculate the degradation rate of methylene blue.
As can be seen from transmission electron microscope picture (Fig. 1 ~ Fig. 4), in new modified graphene-supported titanium dioxide composite photocatalyst prepared by the present invention titanium dioxide granule particle diameter be about 10nm and uniform load on graphene sheet layer.Comparative example 1 adopts in dipping absorption and the graphene-supported titanium dioxide composite photocatalyst prepared by hydro-thermal method equally, graphene sheet layer only has little titanium dioxide granule distribute.Comparative example 2 adopts the standby titanium dioxide of Direct Hydrothermal legal system to be the large spheric granules of particle diameter 150nm.
By finding out the photocatalytic degradation curve (Fig. 5) of methylene blue, compared with the titanium dioxide prepared with same procedure, the photocatalysis performance of new modified graphene-supported titanium dioxide composite photocatalyst obtains and significantly improves.And graphene-supported titanium dioxide composite photocatalyst due to content of titanium dioxide lower, major embodiment goes out absorption property, and photocatalysis performance is but relatively weak.Embodiment sample f-G/T (1), f-G/T (2) and f-G/T (3) topmost difference are that the triethanolamine consumption added in modified graphene oxide preparation process is different, thus cause the modification degree of graphene oxide different, direct affect institute's adsorb oxygen titanium cation number, and then make the titanium dioxide output that generates different.The degradation effect of f-G/T (2) and f-G/T (1) are closely, infer that the modified graphene oxide used by f-G/T (2) is complete close to modification, then the consumption increasing triethanolamine further has little significance to the modification degree improving graphene oxide.F-G/T (3) is comparatively strong to the adsorption capacity of MB, and degradation effect is poor, this is because the modification degree of graphene oxide used by f-G/T (3) is lower, and epontic TiO
2measure less.
Claims (10)
1. the preparation method of a modified graphene carried titanium dioxide composite photo-catalyst, it is characterized in that, Hummers method first by improving obtains graphene oxide suspension, in graphene oxide suspension, add triethanolamine react at 60 ~ 120 DEG C of temperature, obtain modified graphene oxide suspension; Being added to by gained modified graphene oxide hanging drop is dissolved with in the sulfuric acid solution of titanyl sulfate, and after ultrasonic assistant soakage, centrifugation, obtains composite photo-catalyst presoma; Gained composite photo-catalyst presoma joins in alkaline solution, hydro-thermal reaction is carried out at 70 ~ 100 DEG C of temperature, hydro-thermal reaction product after predrying, at 400 ~ 500 DEG C of temperature in air atmosphere calcining reduction, obtain modified graphene carried titanium dioxide composite photo-catalyst.
2. method according to claim 1, is characterized in that, the graphene oxide suspension concentration obtained by the Hummers method improved is 1 ~ 20mg/mL.
3. method according to claim 1, is characterized in that, in described triethanolamine and graphene oxide suspension, the mass ratio of graphene oxide is 1:1 ~ 10:1.
4. method according to claim 1, is characterized in that, the time that graphene oxide and triethanolamine react at 60 ~ 120 DEG C of temperature is 1 ~ 5h.
5. method according to claim 1, is characterized in that, in described sulfuric acid solution, the concentration of sulfuric acid is 0.1 ~ 1mol/L.
6. method according to claim 1, is characterized in that, the time of described ultrasonic assistant soakage is 0.5 ~ 4h.
7. method according to claim 1, is characterized in that, described alkaline solution is the Na of concentration between 0.1 ~ 1mol/L
2cO
3solution, K
2cO
3one or more mixing in solution, NaOH solution, KOH solution.
8. method according to claim 1, is characterized in that, the described hydro-thermal reaction time is 15 ~ 30h.
9. method according to claim 1, is characterized in that, the described calcining reduction time is 1 ~ 5h.
10. the method according to any one of claim 1 ~ 9, is characterized in that, in described modified graphene carried titanium dioxide composite photo-catalyst, the mass percentage of Graphene is between 1 ~ 25%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
| CN102225330A (en) * | 2011-04-20 | 2011-10-26 | 东南大学 | Method for preparing photochemical catalyst/graphene one-dimensional nuclear shell compound structure by using photochemical catalysis method |
| CN102698728A (en) * | 2012-05-14 | 2012-10-03 | 无锡润鹏复合新材料有限公司 | Titanium dioxide nanotube/ graphene composite material and preparation method thereof |
| WO2013062306A2 (en) * | 2011-10-24 | 2013-05-02 | 포항공과대학교 산학협력단 | High purity graphene synthesis melted in water through photocatalytic reaction |
-
2015
- 2015-03-25 CN CN201510133238.6A patent/CN104785235B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
| CN102225330A (en) * | 2011-04-20 | 2011-10-26 | 东南大学 | Method for preparing photochemical catalyst/graphene one-dimensional nuclear shell compound structure by using photochemical catalysis method |
| WO2013062306A2 (en) * | 2011-10-24 | 2013-05-02 | 포항공과대학교 산학협력단 | High purity graphene synthesis melted in water through photocatalytic reaction |
| CN102698728A (en) * | 2012-05-14 | 2012-10-03 | 无锡润鹏复合新材料有限公司 | Titanium dioxide nanotube/ graphene composite material and preparation method thereof |
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