CN102755885B - Hydrothermal preparation method of TiO2-rGO composite photochemical catalyst - Google Patents
Hydrothermal preparation method of TiO2-rGO composite photochemical catalyst Download PDFInfo
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Abstract
The invention relates to a hydrothermal preparation method of a TiO2-rGO composite photochemical catalyst, sequentially comprising the following steps of: dispersing pretreated TiO2 into 10mL of graphene oxide solution prepared by step 2), and evenly stirring, so as to obtain stable TiO2-GO suspending liquid; and carrying out hydrothermal treatment under the temperature of 100-200DEG C for 0.5-10 hours, washing a product by three times, and carrying out vacuum drying, so as to obtain the TiO2-rGO composite photochemical catalyst. The hydrothermal preparation method has the benefit effects of taking purified water as a solvent, being simple to operate, and free from adding various reducing agents such as an organic surface active agent and an additive, thereby being a green and environment-friendly graphene oxide reduction method. The photoproduction-electron hole effective separation efficiency can be improved due to the high electronic mobility of reduced graphene, so that the photocatalysed performance of the TiO2 can be improved, and the hydrothermal preparation method has the advantages of being very simple to operate, low in equipment requirement, free from expressive reaction devices, easy to synthesize on a large scale, etc.
Description
Technical field
The present invention relates to TiO
2the hydrothermal preparing process of-rGO composite photo-catalyst.
Technical background
Day by day serious due to global air and water pollution, application photocatalysis degradation organic contaminant causes increasing concern.Titanium dioxide be study the most widely, there is photocatalytic activity, one of various organic photochemical catalyst of effectively degrading.But, titanium dioxide optical catalyst fails extensive use, under main cause is UV-irradiation light, titanium dioxide can produce photo-generate electron-hole pair, and photo-generate electron-hole produces chemical action soon to the speed of compound than the pollutant of titanium dioxide and absorption, and photocatalysis efficiency is reduced.Therefore, current facing challenges is the compound how effectively stoping electron-hole pair, improves TiO
2photocatalytic activity.A series of modification strategies is applied in TiO
2in based nano composite material, as noble metal loading, zwitterion doping, dyestuff or quantum dot sensitized, with other semiconductors coupling etc.Wherein, modification TiO is carried out with the Graphene with bigger serface and excellent conductivity
2an important research direction is become to strengthen its photocatalysis performance.
Graphene is by carbon atom sp
2the individual layer two dimension graphite-structure that hydridization is formed.Graphene has large specific area, can significantly improve various organic adsorption capacity.In addition, Graphene also has unique electronic property, as high electron mobility (250,000 cm
2v
-1s
-1)), be expected to the effective carrier as light induced electron in photocatalytic process.Result of study shows: be difficult to prepare Graphene on a large scale by machinery or physics stripping method, and solution chemical method can obtain the graphene oxide of favorable dispersibility on a large scale.But because chemical method employs a large amount of strong oxidizers, make surface of graphene oxide create a large amount of oxygen-containing functional groups, cause the electric conductivity of its difference.How the reduced graphene that the graphene oxide of poor electric conductivity changes high conductivity into is become one of important topic in current international research field.Recently, many researchers utilize various method of reducing, as chemical reduction method---use some reducing agent (hydrazine hydrate, sodium borohydride, natrium citricum and vitamin C etc.), solvent-thermal method, ultraviolet light auxiliary law, photo-reduction etc., effectively graphene oxide is reduced to reduced graphene, substantially increase the transmittability of Graphene to electronics, thus extend the application of Graphene.
At present, at Graphene and TiO
2in the preparation process of composite, be adopt to add various additive and carry out redox graphene as the method for reducing agent mostly.As far as we know, also do not find at present about when without the need to any additive as reducing agent, be that water used in solvent hot method one step prepares TiO with pure water
2with reduced graphene compound (TiO
2-rGO) the report of high-activity photocatalyst.
Summary of the invention
Technical problem to be solved by this invention proposes a kind of TiO for above-mentioned prior art
2the hydrothermal preparing process of-rGO composite photo-catalyst, its when without the need to any additive as reducing agent, be that solvent one step prepares high activity TiO with pure water
2-rGO composite photo-catalyst, the composite photo-catalyst of gained shows than pure TiO
2higher photocatalysis performance.
The present invention solves the problems of the technologies described above adopted technical scheme: TiO
2the hydrothermal preparing process of-rGO composite photo-catalyst, is characterized in that including next coming in order step:
1) by 0.5 g business P25 TiO
2pretreatment 0.5-5 h is carried out in 200-800 DEG C;
2) graphene oxide ultrasonic disperse is formed uniform graphene oxide (GO) solution in deionized water, wherein the concentration of graphene oxide is 0.0025-0.5 wt %;
3) by pretreated for step 1) TiO
2be distributed to 10 ml steps 2) in the graphene oxide solution prepared, stir and form stable TiO
2-GO suspension;
4) by the TiO of step 3) gained
2-GO suspension is at 100-200 DEG C of Water Under heat treatment 0.5-10 h, and products therefrom washs 3 times, after vacuum drying, namely obtains TiO
2-rGO composite photo-catalyst.
By such scheme, TiO in step 1)
2pretreatment temperature be preferably 350-600 DEG C, pretreatment time is preferably 1-3h.
By such scheme, step 2) in the concentration of graphene oxide be preferably 0.05-0.25 wt %.
By such scheme, in step 3), the hydrothermal treatment consists temperature of suspension is preferably 120-170 DEG C, and hydrothermal conditions is preferably 2-5 h.
By such scheme, the vacuum drying temperature described in step 4) is 30-100 DEG C, and drying time is 3-12 h.
By such scheme, the vacuum drying temperature described in step 4) is preferably 40-80 DEG C, is preferably 6-8 h drying time.
The present invention propose by hydrothermal method when without the need to any additive as reducing agent, be that solvent one step prepares high activity TiO with pure water
2-rGO composite photo-catalyst, the general principle of its synthesis is: due to the TiO after graphene oxide and heat treatment
2all there is fabulous hydrophily, make TiO
2nano particle is easy to be distributed to surface of graphene oxide and forms uniform suspension; In hydrothermal treatment process, TiO
2directly there is deoxygenation and form reduced graphene in the graphene oxide of nanoparticle surface, causes TiO
2the one-step synthesis of-rGO composite photo-catalyst.
TiO
2the photocatalytic activity of-rGO composite photo-catalyst is characterized by Photocatalytic Degradation of Phenol solution under ultraviolet light.Experimentation is as follows: by 0.05 g TiO
2-rGO composite photo-catalyst is dispersed in and 10 mL phenol solution (10 mgL is housed
-1) culture dish in (diameter is 5 cm), culture dish is positioned over dark place 2 h to reach adsorption equilibrium.At ambient temperature, with the ultra violet lamp of 15 W, measure the phenol concentration in solution every 15 min.In degradation solution, the concentration of phenol is measured by ultraviolet-visible absorption spectroscopy instrument (UVmini 1240, Japan).
TiO
2the Characterization for Microstructure method of-rGO composite photo-catalyst: observe pattern and granular size with field emission scanning electron microscope (FESEM), by X-ray diffraction (XRD) spectrum analysis crystallization situation, by the reduction situation of infrared spectrum (FTIR) and Raman spectrum analysis graphene oxide.The photoelectron spectrograph (KRATOA XSAM800 XPS) being X-ray source at Mg target K α obtains x-ray photoelectron energy spectrogram, determines component and valence state.
Beneficial effect of the present invention is: of the present invention take pure water as the method for solvent, simple to operate, without the need to adding the reducing agents such as various organic surface active agent, additive, is a kind of graphene oxide method of reducing of environmental protection.The electron mobility that reduced graphene is high can improve the effective separative efficiency of photo-generate electron-hole, thus improves TiO
2photocatalysis performance.As commercialization P25 TiO
2with when containing 1-5% Graphene in graphene composite photocatalyst, the Photocatalytic Degradation Property of Pyrogentisinic Acid is than pure commercialization P25 TiO under ultraviolet light
2improve 20%-30%.The present invention has that operation is very simple, equipment requirement is low, without the need to costliness various reaction units, be easy to the advantages such as synthesis in enormous quantities.
Accompanying drawing explanation
fig. 1for TiO in embodiment 1
2the synthesis schematic diagram of-rGO composite;
fig. 2for graphene oxide, reduced graphene, TiO in embodiment 1
2and TiO
2x-ray diffraction (XRD) spectrogram of-rGO composite: (a) GO; (b) rGO; (c) TiO
2; (d) TiO
2-rGO (1 wt %);
fig. 3for graphene oxide, TiO in embodiment 1
2and TiO
2field emission scanning electron microscope (FESEM) figure: (a) GO of-rGO composite; (b) TiO
2; (c) TiO
2-rGO (1 wt %);
fig. 4for graphene oxide, reduced graphene, TiO in embodiment 1
2and TiO
2infrared spectrum (FTIR) figure: (a) GO of-rGO composite; (b) rGO; (c) TiO
2; (d) TiO
2-rGO (1 wt %);
fig. 5for TiO in embodiment 1
2, graphene oxide, reduced graphene and TiO
2the Raman spectrogram of-rGO composite: (a) TiO
2; (b) GO; (c) rGO; (d) TiO
2-rGO (1 wt %);
fig. 6for graphene oxide, reduced graphene and TiO in embodiment 1
2the C1s spectrogram of the x-ray photoelectron power spectrum (XPS) of-rGO composite: (a) GO; (b) rGO; (c) TiO
2-rGO (1 wt %);
fig. 7for TiO in embodiment 1
2and TiO
2the speed constant of-rGO composite degradation of phenol under ultraviolet light
k: (a) TiO
2; (b) TiO
2-rGO (1 wt %).
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described in detail, but this explanation can not be construed as limiting the invention.
embodiment 1:
TiO
2the preparation process of-rGO composite photo-catalyst is as follows: (1) is by 0.5 g business P25 TiO
2through 550 DEG C of pretreatment 2 h; (2) form uniform graphene oxide (GO) solution after graphene oxide being dissolved in deionized water for ultrasonic process, wherein the concentration of graphene oxide is 0.05 wt %; (3) the pretreated TiO of 0.5 g
2be distributed in 10 ml graphene oxide solution, stir 2 h, form stable TiO
2-GO suspension; (4) by the TiO of above-mentioned preparation
2-GO suspension is placed in 150 DEG C of Water Under heat treatment 5 h; After products therefrom washs 3 times, at 60 DEG C of vacuum drying 6 h, namely obtain TiO
2-rGO composite photo-catalyst.
Fig. 1 is TiO
2the synthesis schematic diagram of-rGO composite.As everyone knows, because graphene oxide contains a lot of oxygen-containing functional group, as-OH, C=O, C-O-C and-COOH, so it can be scattered in water well form even and stable solution.Fig. 1 a is graphene oxide structural representation, can find out that graphene oxide is brown color from its optics picture; Fig. 1 b is TiO
2with the mixture of graphene oxide, TiO can be found out
2be dispersed in well in graphene oxide solution, due to the TiO added
2white powder, so mixed solution is light yellow; Fig. 1 c is TiO after hydrothermal treatment consists
2with graphene composite material.Can find out that Graphene becomes black by brown color before and after hydro-thermal, illustrate that graphene oxide is reduced.By to TiO
2hydrothermal treatment consists simple with graphene oxide, obtains a series of TiO
2with redox graphene composite.Illustrate and be easy to graphene oxide to be reduced to reduced graphene under certain hydrothermal condition, meanwhile, TiO
2granular composite on graphenic surface.
Fig. 2 is the TiO of preparation
2the XRD collection of illustrative plates of-rGO composite.Clearly, hydrothermal treatment consists rear oxidation Graphene (Fig. 2 a) 2
θ=11.0 characteristic peaks disappear, and occur 2 in reduced graphene (Fig. 2 b)
θ=24.1(002) characteristic peak of crystal face, illustrate that graphene oxide is successfully reduced.And it should be noted that TiO
2-rGO composite (Fig. 2 d) has and TiO
2the XRD collection of illustrative plates that (Fig. 2 c) characteristic diffraction peak is similar.At TiO
2with the diffraction maximum not having in the composite of Graphene to find to belong to separately Graphene feature, reason may be that content is limited in the composite for Graphene.
Fig. 3 is graphene oxide, TiO
2and TiO
2the FESEM figure of-rGO composite.Fig. 3 a is the SEM figure of graphene oxide, and graphene oxide is thin and curling structure as can be seen from Fig..Little and the TiO be evenly distributed of particle diameter can be seen from Fig. 3 b
2particle.And can to find out that after hydro-thermal Graphene also maintains the curling pattern of thin stratiform and at a lot of TiO of its surface distributed from Fig. 3 c
2particle, size is at about 30 nm.Show TiO
2with the success between Graphene defines strong chemical bond, likely improve the photocatalytic activity of composite.
Fig. 4 is graphene oxide, reduced graphene, TiO
2and TiO
2the infrared spectrum of-rGO composite.(Fig. 4 a) demonstrates very strong absworption peak owing to having many oxygen-containing functional groups to graphene oxide, as stretching vibration peak (3410 cm of hydroxyl-OH waterborne
-1place), carbonyl C=O stretching vibration peak (1734 cm
-1place), the flexural vibrations peak of-OH of water and C=C stretching vibration peak (1629 cm
-1place), C-OH flexural vibrations peak (1420 cm
-1place), epoxy stretching vibration peak C-O-C and C-O(1227 cm
-1place) and carboxylic acid on C-O stretching vibration peak (1055 cm
-1place).Compared with graphene oxide ,-OH vibration peak, 1734 cm of water in redox graphene (Fig. 4 b)
-1c=O peak, 1055 cm at place
1the C-O peak at place and 800-1500 cm
-1the intensity in peak district all obviously declines, and graphene oxide success deoxidation is described and is reduced to reduced graphene.TiO
2in the infrared spectrogram of (Fig. 4 c) except showing the flexible and flexural vibrations of-OH in water, also at lower wave number district (400-900 cm
-1) there is TiO
2ti-O-Ti key.TiO
2the situation of oxygen-containing functional group and the similar of rGO in-rGO composite (Fig. 4 d), show graphene oxide after hydrothermal treatment consists in composite successful transformation be reduced graphene.In addition at lower wave number district 400-900 cm
-1, TiO
2-rGO composite shows wider absorption, mainly due to TiO
2ti-O-Ti key and the new Ti-O-C key acting in conjunction formed cause.Therefore, above-mentioned result of study confirms successful reduction and the TiO of graphene oxide
2the successful synthesis of-rGO composite.
The TiO that the Raman spectrum of Fig. 5 can provide
2with the structural information of Graphene.TiO
2(Fig. 5 a) in structure Raman peaks at 144 cm
-1(E
g), 395 cm
-1(B
1g), 516 cm
-1(A
1g) and 639 cm
-1(E
g) demonstrate very strong characteristic peak.And work as TiO
2with (Fig. 5 d) after Graphene compound, these characteristic peaks significantly weaken, and may be because graphene coated is at TiO
2surface, part masks TiO
2raman information.This demonstrate between composite and define very strong chemical action.Raman spectrum is also a strong and carbon atom sp in widely used sign Graphene
2and sp
3hybrid structure defect.The illustration display of Fig. 5, at 1347 cm
-1with 1590 cm
-1place finds D peak and the G peak of Graphene and composite thereof.D peak is by sp
3the carbon of hydridization type causes, and show as structural defect and unordered degree, and G peak is by sp in Graphene
2the carbon of hydridization type causes, and shows as the integrated degree in graphene-structured in Graphene.And the strength ratio at D peak and G peak reflects the defect of Graphene and unordered degree usually.By Fig. 5 result, calculate the I of graphene oxide
d/ I
g0.807, and the I of reduced graphene
d/ I
gbe 0.925 higher than graphene oxide, show that graphene oxide is reduced to reduced graphene in the composite.On the other hand, TiO can be found out
2have an appointment 10 cm for the G peak of-rGO composite
-1change.Therefore, be all provide tangible proof for the reduction of graphene oxide and graphene composite material successfully synthesize at the change of raman spectrum strength and G peak blue shift.
Fig. 6 is graphene oxide, reduced graphene and TiO
2the C 1s spectrogram of the x-ray photoelectron power spectrum (XPS) of-rGO composite.There is the carbon bond of Four types in display in the C 1s spectrogram of XPS, that is: C – C, C=C, C-H (284.9 eV), C-O-C, C-OH (286.6 eV), C=O (287.6 eV) and O=C-OH (288.3 eV).Graphene oxide (Fig. 6 C-C a), C=C and c h bond and oxygen containing carbon bond C-O (286.6 eV) and C=O (288.3 eV) intensity all very high.In reduced graphene (Fig. 6 b), oxygen containing carbon bond intensity obviously declines, and meanwhile, as can be seen from Table 1 compared with graphene oxide, the ratio shared by peak area of the CC key of reduced graphene is increased to 0.62 from 0.42.But C-O-C and O=C-OH proportion drops to 0.14 and 0.19 from 0.32 respectively and drops to 0.03.This shows that water-heat process decreases the content of C-O key, thus makes graphene oxide change reduced graphene into.From TiO
2can find out similar to reduced graphene in the C1s spectrogram of the XPS of-rGO composite (Fig. 6 c), it also correspondingly reduces containing oxygen carbon bond ratio.Above result shows that Hydrothermal Synthesis can significantly reduce carbon-oxygen bond content, thus makes graphene oxide be converted to reduced graphene and for TiO
2in-rGO composite, the reduction of GO further provides strong evidence.
Fig. 7 is TiO
2and TiO
2the degradation rate constant column diagram of-rGO composite degradation of phenol aqueous solution under ultraviolet light.As can be seen from the figure, the content of Graphene is to TiO
2photocatalysis performance have significant impact.After introducing a small amount of Graphene, sample TiO
2-rGO(1 wt %) photocatalysis performance of (Fig. 7 b) is than pure TiO
2(Fig. 7 a) obviously strengthens, and reaction rate constant is 4.7 × 10
-3min
-1.TiO
2the principle of-rGO composite photocatalyst performance enhancement is: first, and Graphene has excellent absorption property owing to having large specific area, thus adds organic concentration near catalyst surface.Phenol molecule is transferred to catalyst surface from solution and can be connected with Graphene conjugation.Therefore with pure TiO
2compare, TiO
2-rGO composite Pyrogentisinic Acid has higher adsorption rate.Secondly, titanium dioxide, after ultraviolet excitation, produces electron-hole pair.After Graphene compound, the electrons on titanium dioxide conduction band is quickly transferred on Graphene, effectively reduces the compound in electronics and hole.Therefore, the strong adsorption capacity of Graphene and the fast transport of charge carrier facilitate the degraded of photochemical catalyst to dyestuff.
embodiment 2:
In order to check TiO
2powder pre-treating temperature is to TiO
2the impact of-rGO nano composite material, except pretreatment temperature difference, other reaction conditions are as follows: TiO
2powder pre-treating time (2 h), TiO
2(0.5 g), (2 h), (5 h), baking temperature (60 DEG C), drying time, (6 is h) etc. all identical with embodiment 1 hydrothermal temperature (150 DEG C), hydro-thermal time for graphene oxide concentration (0.05 %) and volume (10 milliliters), mixing time for powder quality.Result shows, pretreatment temperature 200 DEG C time, TiO
2the impurity that powder surface adsorbs fails effectively to remove, and after mixing with graphene solution, uniformity and suspendability poorly, have impact on TiO
2with the combination of Graphene; Pretreatment temperature when 350-600 DEG C, TiO
2powder mixes with graphene solution, obtains dissolution homogeneity and suspendability is all fine; When pretreatment temperature reaches 800 DEG C, TiO
2powder particle is excessive, is unfavorable for being dispersed in the solution of graphene oxide, easily coagulation occurs.Therefore, TiO
2in the building-up process of-rGO nano composite photo-catalyst, TiO
2powder pre-treating optimum temperature is 350-600 DEG C.
embodiment 3:
In order to check TiO
2the powder pre-treating time is to TiO
2the impact of-rGO nano composite material, except pretreatment time difference, other reaction conditions are as follows: TiO
2powder pre-treating temperature (550 DEG C), TiO
2(0.5 g), (2 h), (5 h), baking temperature (60 DEG C), drying time, (6 is h) etc. all identical with embodiment 1 hydrothermal temperature (150 DEG C), hydro-thermal time for graphene oxide concentration (0.05 %) and volume (10 milliliters), mixing time for powder quality.Result shows, when pretreatment time is 0.5 h, and TiO
2the impurity that powder surface adsorbs fails effectively to remove, and have impact on formation and the TiO of composite
2with the combination of Graphene; When pretreatment time is 1-3 h, TiO
2the impurity that powder surface adsorbs effectively is removed, and defines fresh surfaces, makes TiO
2combine with graphenic surface and be easy to carry out; When pretreatment time reaches 5 h, TiO
2powder particle is excessive, is unfavorable for being dispersed in graphene oxide solution forming suspension, easily coagulation occurs.Therefore, TiO
2in the building-up process of-rGO nano composite photo-catalyst, TiO
2powder pre-treating Best Times is 1-3 h.
embodiment 4:
In order to check Graphene concentration to TiO
2the impact of-rGO nano composite material photocatalysis performance, except Graphene concentration difference, other reaction conditions are as follows: TiO
2powder pre-treating temperature (550 DEG C), TiO
2powder pre-treating time (2 h), TiO
2(0.5 g), (2 h), (5 h), baking temperature (60 DEG C), drying time, (6 is h) etc. all identical with embodiment 1 hydrothermal temperature (150 DEG C), hydro-thermal time for graphene oxide volume (10 milliliters), mixing time for powder quality.Result shows, when Graphene concentration is 0.0025%, Graphene content is very few to TiO
2photocatalysis performance does not have a significant effect; When Graphene concentration is 0.05%-0.25 %, the TiO of gained
2the performance of-rGO composite photo-catalyst has obvious humidification, and the Photocatalytic Degradation Property of Pyrogentisinic Acid is than pure commercialization P25 TiO under ultraviolet light
2improve 20%-30%; When Graphene concentration is 0.5%, the photocatalytic activity of too much Graphene sample is than pure TiO
2low.This may be due to TiO
2-rGO composite is to the increase of the scattering of light, and the Graphene of high-load is blinded by the absorption of coated titanium dioxide to ultraviolet light, results through the rapid minimizing of reactant liquor exciting light.Therefore, TiO
2in the building-up process of-rGO nano composite photo-catalyst, graphene oxide optimum concentration range is 0.05%-0.25 %.
embodiment 5:
In order to check hydrothermal temperature to TiO
2the impact of-rGO nano composite material photocatalysis performance, except hydrothermal temperature difference, other reaction conditions are as follows: TiO
2powder pre-treating temperature (550 DEG C), TiO
2powder pre-treating time (2 h), TiO
2(0.5 g), (2 h), (5 h), baking temperature (60 DEG C), drying time, (6 is h) etc. all identical with embodiment 1 hydrothermal temperature (150 DEG C), hydro-thermal time for graphene oxide concentration (0.05%) and volume (10 milliliters), mixing time for powder quality.Result shows, when hydrothermal temperature is 100 DEG C, graphene oxide is reduced degree to be reduced greatly; When hydrothermal temperature is respectively 120 DEG C, 150 DEG C, 170 DEG C, graphene oxide can be reduced; When hydrothermal temperature is higher than 180 DEG C, when reaching 200 DEG C, Graphene and compound generation carbonization thereof.Therefore, TiO
2in the building-up process of-rGO nano composite photo-catalyst, the optimum temperature of hydro-thermal is 120-170 DEG C.
embodiment 6:
In order to check the hydro-thermal time to TiO
2the impact of-rGO nano composite material, except hydro-thermal time difference, other reaction conditions are as follows: TiO
2powder pre-treating temperature (550 DEG C), TiO
2powder pre-treating time (2 h), TiO
2(0.5 g), (2 h), hydrothermal temperature (150 DEG C), baking temperature (60 DEG C), drying time, (6 is h) etc. all identical with embodiment 1 for graphene oxide concentration (0.05%) and volume (10 milliliters), mixing time for powder quality.Result shows, the hydro-thermal time is relevant with hydrothermal temperature.Hydrothermal temperature is 150 DEG C, and when the hydro-thermal time is 0.5 h, the degree that graphene oxide is reduced reduces greatly; When the hydro-thermal time is 2-5 h, graphene oxide can be reduced more complete; When the hydro-thermal time reaches 10 h, Graphene and compound pattern thereof and photocatalysis performance all significantly do not change.Therefore, TiO
2in the building-up process of-rGO nano composite photo-catalyst, collateral security Graphene reducing degree and the angle that saves time are considered, hydro-thermal reaction time optimal is 2-5 h.
embodiment 7:
In order to check baking temperature to TiO
2the impact of-rGO nano composite material, except baking temperature difference, other reaction conditions are as follows: TiO
2powder pre-treating temperature (550 DEG C), TiO
2powder pre-treating time (2 h), TiO
2(0.5 g), (2 h), (5 h), drying time, (6 is h) etc. all identical with embodiment 1 hydrothermal temperature (150 DEG C), hydro-thermal time for graphene oxide concentration (0.05%) and volume (10 milliliters), mixing time for powder quality.Result shows, when baking temperature is 30 DEG C, and TiO
2the complete baking needed of-rGO composite material granular chronic; When baking temperature is 40-80 DEG C, TiO
2the time of the complete baking needed of-rGO composite material granular is appropriate; When baking temperature reaches 100 DEG C, TiO
2-rGO composite material granular easily hardens into relatively large body.Therefore, TiO
2in the building-up process of-rGO nano composite photo-catalyst, dry optimum temperature is 40-80 DEG C.
embodiment 8:
In order to check drying time to TiO
2the impact of-rGO nano composite material, except drying time difference, other reaction conditions are as follows: TiO
2powder pre-treating temperature (550 DEG C), TiO
2powder pre-treating time (2 h), TiO
2(0.5 g), (2 h), (5 h), baking temperature (60 DEG C) etc. is all identical with embodiment 1 hydrothermal temperature (150 DEG C), hydro-thermal time for graphene oxide concentration (0.05%) and volume (10 milliliters), mixing time for powder quality.Result shows, TiO
2the drying time of-rGO nanocomposite particles is relevant with baking temperature.When baking temperature is 60 DEG C, be 3 h when drying, sample does not parch, and also contains comparatively juicy; Be 6-8 h when drying, sample parches; Be after 12 h when drying, quality and the character of Graphene and compound thereof significantly do not change.Therefore, TiO
2in the building-up process of-rGO nano composite photo-catalyst, collateral security sample bone dry and the angle that saves time are considered, when baking temperature is 60 DEG C, best drying time is 6-8 h.
Containing the peak area of oxygen carbon bond and the ratio of the gross area in table 1 XPS
| Sample | A C-C/A | A C-O/A | A C=O/A | A COOH/A |
| GO | 0.42 | 0.32 | 0.07 | 0.19 |
| rGO | 0.62 | 0.14 | 0.21 | 0.03 |
| TiO 2-rGO (1 wt %) | 0.86 | 0.10 | 0.04 | 0 |
Claims (4)
1.TiO
2the hydrothermal preparing process of-rGO composite photo-catalyst, is characterized in that including next coming in order step:
1) by 0.5 g business P25 TiO
2pretreatment 0.5-5 h is carried out in 200-800 DEG C;
2) graphene oxide ultrasonic disperse is formed uniform graphene oxide (GO) solution in deionized water, wherein the concentration of graphene oxide is 0.0025-0.5 wt %;
3) by pretreated for step 1) TiO
2be distributed to 10 ml steps 2) in the graphene oxide solution prepared, stir and form stable TiO
2-GO suspension;
4) by the TiO of step 3) gained
2-GO suspension is at 100-200 DEG C of Water Under heat treatment 0.5-10 h, and products therefrom washs 3 times, after vacuum drying, namely obtains TiO
2-rGO composite photo-catalyst, described vacuum drying temperature is 40-80 DEG C, and drying time is 6-8 h.
2. TiO as claimed in claim 1
2the hydrothermal preparing process of-rGO composite photo-catalyst, is characterized in that TiO in step 1)
2pretreatment temperature be 350-600 DEG C, pretreatment time is 1-3h.
3. TiO as claimed in claim 1 or 2
2the hydrothermal preparing process of-rGO composite photo-catalyst, is characterized in that step 2) in the concentration of graphene oxide be 0.05-0.25 wt %.
4. TiO as claimed in claim 1 or 2
2the hydrothermal preparing process of-rGO composite photo-catalyst, it is characterized in that the hydrothermal treatment consists temperature of suspension in step 4) is 120-170 DEG C, hydrothermal conditions is 2-5 h.
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