CN104399457B - A kind of Au/TiO2/ CFP tri compound nano-photocatalyst and preparation method thereof and application - Google Patents
A kind of Au/TiO2/ CFP tri compound nano-photocatalyst and preparation method thereof and application Download PDFInfo
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Abstract
The invention belongs to composite photocatalyst material preparation and application, be specifically related to a kind of Au/TiO2/ CFP tri compound nano-photocatalyst and preparation method thereof and application. The present invention prepares TiO in infiltration-hydro-thermal reaction method2On the basis of/CFP binary composite photo-catalyst, prepare Au/TiO by uv irradiation method further2/ CFP tri compound nano-photocatalyst. Volatile organic matter is not only had stronger absorption property by this photocatalyst, and there is stronger visible light catalysis activity, it is achieved thereby that the absorption of volatile organic matter is integrated with photocatalysis mineralising, it is greatly enhanced reaction rate and the efficiency of photocatalysis degradation organic contaminant, can apply at field of Environment Protection as adsorbent or photocatalyst.
Description
Technical field
The invention belongs to composite photocatalyst material preparation and application, be specifically related to a kind of Au/TiO2/ CFP tri compound nano-photocatalyst and preparation method thereof and application.
Background technology
Volatile organic matter is one of major pollutants in industrial occupancy and urban air, it is possible to surrounding and health are caused serious harm. For this, people have been developed over the physics of multiple removal volatile organic matter, chemistry and biological method. Wherein, titanium dioxide (TiO2) photocatalysis oxidation technique as a kind of emerging depollution of environment technology, receive extensive concern. TiO2There is Stability Analysis of Structures, photocatalysis efficiency height and lower-price characteristic, can be used for the high efficiency photocatalyst of the depollution of environment. Under irradiation under ultraviolet ray, TiO2Can at room temperature produce the hole with Strong oxdiative ability, volatile organic matter is completely decomposed into CO2And H2O. But, TiO2Photocatalyst applications also has some shortcomings part. First, TiO2Light-catalyzed reaction need use ultraviolet light, the utilization rate of visible ray is low. Secondly, material excites the recombination process of electronics and hole, it is possible to reduce the activity of photocatalyst. Finally, TiO2The specific surface area of material is less, to organic limited sorption capacity. The above all limits TiO2Application in the depollution of environment.
Carbon fiber paper (CFP) is a kind of carbonaceous material assembled that interlocked by carbon fiber, it may be possible to TiO2One of excellent carrier of photocatalyst. CFP has three-dimensional porous structure, it is possible to provides higher specific surface area for organic absorption, and increases light-catalysed avtive spot. CFP also has higher electric conductivity and electron storage capacitance, it is possible to accept TiO2Produced light induced electron, stops the compound of electronics and hole. Therefore, CFP and TiO2Between interaction be TiO2The improvement of properties of catalyst provides new opportunity. Meanwhile, noble metal Au and TiO2Compound tense, it is possible to absorb visible ray in quantized mode by Au particle surface plasma resonance, is conducive to photocatalyst to the absorption of visible ray and utilization.But, at present about CFP, Au and TiO2The preparation of Three-element composite photocatalyst and application in photocatalytic degradation volatile organic matter have not been reported.
Summary of the invention
In order to overcome the deficiencies in the prior art and shortcoming, the primary and foremost purpose of the present invention is in that to provide a kind of Au/TiO2The preparation method of/CFP tri compound nano-photocatalyst.
Another object of the present invention is to the Au/TiO providing said method to prepare2/ CFP tri compound nano-photocatalyst.
It is still another object of the present invention to provide above-mentioned Au/TiO2The application of/CFP tri compound nano-photocatalyst.
The purpose of the present invention is realized by following proposal:
A kind of Au/TiO2The preparation method of/CFP tri compound nano-photocatalyst, comprises the steps of:
(1) carbon fiber paper (CFP) is immersed in dense HNO3With dense H2SO4In the nitration mixture of composition, reflux 30��180min at 85��95 DEG C, is washed out to neutrality, by the drying precipitate after washing, obtains the carbon fiber paper after purification;
(2) butyl titanate is joined in ethanol, after stirring, obtain the settled solution of the butyl titanate that concentration is 2��50g/L;
(3) carbon fiber paper after the purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, dry; Repeat moistening and dry run 2��5 times, obtain butyl titanate solution-wet dried carbon fiber paper;
(4) the mixing suspension of preparation NaOH and titanium dioxide, the wherein final concentration of 50��200g/L of NaOH, the final concentration of 4��20g/L of titanium dioxide;
(5) the butyl titanate solution-wet of step (3) gained dried carbon fiber paper are added in step (4) in the mixing suspension of gained hydro-thermal reaction 6��48h at 90��150 DEG C; Products therefrom cyclic washing, to neutral, by the drying precipitate after washing, obtains TiO2/ CFP binary composite photo-catalyst;
(6) by the TiO of step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl that concentration is 5��15g/L4In aqueous solution, lucifuge stands 0.5��5h, then is placed under ultraviolet and irradiates 1��5h; Taking out product, cyclic washing, to neutral, by the drying precipitate after washing, obtains Au/TiO2/ CFP tri compound nano-photocatalyst;
The Functionality, quality and appealing design of the carbon fiber paper described in step (1) elects 0.5��10g as; The volume of described nitration mixture is preferably 4��200mL; Described dense HNO3Mass fraction be 69%; Described dense H2SO4Mass fraction be 98%; Dense HNO in described nitration mixture3With dense H2SO4Volume ratio be preferably 1:(1��5); Described baking temperature is preferably 50��180 DEG C; Drying time is preferably 3��12h; The solvent of described washing is preferably water; Described mode of washing is preferably filtration washing;
The Functionality, quality and appealing design of the tetraethyl titanate described in step (2) elects 0.05��5g as; Ethanol volume described in step (2) is preferably 10��200mL;
Carbon fiber paper after purification described in step (3) is preferably 0.01��1g; Baking temperature described in step (3) is preferably 50��180 DEG C, and drying time is preferably 10��30min;
The mixing suspension of the NaOH described in step (4) and titanium dioxide obtains preferably by ultrasonic disperse;
The Functionality, quality and appealing design of the butyl titanate solution-wet described in step (5) dried carbon fiber paper elects 0.01��1g as; The volume of described mixing suspension is preferably 5��100mL; The solvent of described washing is preferably water; Described mode of washing is preferably centrifuge washing; Described baking temperature is preferably 50��180 DEG C, and drying time is preferably 3��24h;
TiO described in step (6)2The Functionality, quality and appealing design of/CFP binary composite photo-catalyst elects 0.01��1.0g as; Described HAuCl4The volume of aqueous solution is preferably 5��50mL; Described baking temperature is preferably 50��180 DEG C, and drying time is preferably 3��24h; Cleaning solvent described in step (6) is preferably water;
A kind of Au/TiO2/ CFP tri compound nano-photocatalyst, prepares according to above-mentioned preparation method; Described Au/TiO2In/CFP tri compound nano-photocatalyst, diameter be 5��10 microns carbon fiber surface by diameter be 20��60 nanometers, fully wrapped around up to the titanium dioxide nano thread of a few micrometers, and the gold nano grain having particle size to be 2��10 nanometers is dispersed in the surface of carbon fiber and titanium dioxide nano thread; Its X-ray diffraction spectra, laser Raman spectroscopy and x-ray photoelectron power spectrum show that three kinds of elements of C, Ti and Au coexist in catalyst. UV-Vis DRS spectrum then shows that this tri compound nano-photocatalyst has superior Uv and visible light absorbent properties.
The present invention prepares TiO in infiltration-hydro-thermal reaction method2On the basis of/CFP binary composite, prepare Au/TiO by uv irradiation method further2/ CFP tri compound nano-photocatalyst. Volatile organic matter is not only had stronger absorption property by this photocatalyst, and there is stronger visible light catalysis activity, it is achieved thereby that the absorption of volatile organic matter is integrated with photocatalysis mineralising, it is greatly enhanced reaction rate and the efficiency of photocatalysis degradation organic contaminant, can apply at field of Environment Protection as adsorbent or photocatalyst.
The mechanism of the present invention is: by step (1), carbon fiber paper is carried out nitration mixture acidification, removes the impurity of absorption on carbon fiber paper, obtains the carbon fiber paper after purification; Adhere to one layer of titanium oxide by step (2) and step (3) at carbon fiber paper surface, and it can be used as the original position that next step titanium dioxide nano thread grows; Start to generate titanium dioxide nano thread in the titanium oxide layer of carbon fiber paper surface by step (4) and step (5), these nano wires are long in carbon fiber paper surface length, interlaced, whole carbon fiber paper surface is completely covered gradually, forms TiO2/ CFP binary complex; The titanium ion of a large amount of positively charged and electronegative oxonium ion is had due to titanium dioxide surface, therefore can active adsorption HAuCl4AuCl in aqueous solution4 -And Au3+Ion, and Au simple substance will be become containing Au species photo catalytic reduction by step (6), these simple substance Au will be deposited on titanium dioxide surface, forms Au/TiO2/ CFP ternary complex.
Compared to the prior art the present invention, has the advantage that and beneficial effect:
(1) the quantization mode of visible ray is absorbed and TiO by the present invention by carbon fiber paper by the adsorption and enrichment effect of volatile organic matter, Au2The photocatalysis mineralization of nano wire combines, and prepares a kind of new and effective tri compound nano-photocatalyst.
(2) Au/TiO that the present invention prepares2Volatile organic matter gaseous benzene ethylene is shown good absorption and visible light catalysis activity by/CFP tri compound nano-photocatalyst: to the cinnamic degradation rate of the gas phase that initial concentration is 25 �� 1.5ppmv up to 90.7% in 180min, it is achieved thereby that the absorption of volatile organic matter is integrated with visible light catalytic oxidation, make catalyst can mineralizing and degrading adsorbing material adsorbs, is enriched with effectively volatile organic matter, be greatly enhanced reaction rate and the efficiency of visible light photocatalytic degradation of organic pollutants.
(3) Au/TiO of the present invention2/ CFP tri compound nano-photocatalyst at the field of Environment Protection photocatalyst as degraded volatile organic matter, can have wide range of application.
Accompanying drawing explanation
Fig. 1 is Au/TiO2X-ray powder diffraction (XRD) spectrogram of/CFP tri compound nano-photocatalyst.
Fig. 2 is scanning electron microscope (SEM) figure of carbon fiber paper (CFP).
Fig. 3 is TiO2Scanning electron microscope (SEM) figure of/CFP binary composite photo-catalyst.
Fig. 4 is Au/TiO2The scanning electron microscope SEM figure of/CFP tri compound nano-photocatalyst.
Fig. 5 is Au/TiO2Transmission electron microscope (TEM) figure of/CFP tri compound nano-photocatalyst.
Fig. 6 is Au/TiO2/ CFP tri compound nano-photocatalyst is to the cinnamic adsorption breakthrough curve of gas phase and kinetics of photocatalytic degradation curve chart.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The dense HNO related in embodiment3Mass fraction be 69%, dense H2SO4Mass fraction be 98%;
Embodiment 1
(1) 1g carbon fiber paper is joined the dense HNO of 40mL3With dense H2SO4In the nitration mixture that (volume ratio is 1:3) forms, 90 DEG C of backflow 90min, it is washed to neutrality, dries 12h, obtain the carbon fiber paper after purification for 80 DEG C, standby;
(2) 0.7g butyl titanate adds in 20mL ethanol, and stirring 1min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 0.5g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 80 DEG C dry 20min; Such moistening drying course is repeatedly performed 5 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 4.0gNaOH, 0.4gD25 titania powder adds in 20mL deionized water, and ultrasonic disperse 20min obtains the mixing suspension of NaOH and titanium dioxide;
(5) the butyl titanate solution-wet of 0.5g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 110 DEG C of hydro-thermal reaction 48h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 8h, obtain TiO for 80 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.5g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 10mL, 10g/L4In aqueous solution, lucifuge stands 1h, then is placed on the high voltage mercury lamp radiation 2h of optical wavelength 365nm; After reaction terminates, take out product and be washed to neutrality, drying 24h, obtain Au/TiO for 80 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity is tested: weigh the Au/TiO obtained by 0.5g2/ CFP tri compound nano-photocatalyst is placed in photo catalysis reactor (ACSAppl.Mater.Interfaces2012,4,5988-5996), and before reaction, lucifuge stands 900min, to reach adsorption/desorption balance; The light source used is 300W xenon lamp, and uses optical filter UV filter, after illumination starts, takes 0.2mL gaseous sample every 5min, utilizes and analyzes concentration of substrate change in the gas chromatograph being equipped with flame ionization detector, adopts C/C0Evaluating degradation rate, wherein C is the concentration of styrene of sample, C after illumination certain time0Initial concentration of styrene for sample. After light application time 180min, the cinnamic degradation rate of gaseous state is up to 90.7%.
Embodiment 2
(1) 10g carbon fiber paper is joined the dense HNO of 200mL3With dense H2SO4In the nitration mixture that (volume ratio is 1:1) forms, 85 DEG C of backflow 180min, it is washed to neutrality, dries 3h, obtain the carbon fiber paper after purification for 180 DEG C, standby;
(2) 5g butyl titanate adds in 200mL ethanol, and stirring 2min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 1g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 180 DEG C dry 10min; Such moistening drying course is repeatedly performed 4 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 5.0gNaOH, 0.4gD25 titania powder adds in 100mL deionized water, and ultrasonic disperse 60min obtains the mixing suspension of NaOH and titanium dioxide;
(5) the butyl titanate solution-wet of 1g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 130 DEG C of hydro-thermal reaction 36h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 24h, obtain TiO for 120 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 1g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 50mL, 15g/L4In aqueous solution, lucifuge stands 5h, then is placed on the high voltage mercury lamp radiation 5h of optical wavelength 365nm; After reaction terminates, take out product and be washed to neutrality, drying 12h, obtain Au/TiO for 120 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 1g, and lucifuge stands 720min; After illumination 180min, the cinnamic degradation rate of gaseous state is up to 91.0%.
Embodiment 3
(1) 0.5g carbon fiber paper is joined the dense HNO of 4mL3With dense H2SO4In the nitration mixture that (volume ratio is 1:5) forms, 95 DEG C of backflow 30min, it is washed to neutrality, dries 10h, obtain the carbon fiber paper after purification for 50 DEG C, standby;
(2) 0.05g butyl titanate adds in 10mL ethanol, and stirring 10min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the purification of 0.01g step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 50 DEG C dry 30min; Such moistening drying course is repeatedly performed 5 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 0.5gNaOH, 0.04gD25 titania powder adds in 10mL deionized water, and ultrasonic disperse 1min obtains the mixing suspension of NaOH and titanium dioxide;
(5) the butyl titanate solution-wet of 0.01g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 150 DEG C of hydro-thermal reaction 6h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 12h, obtain TiO for 50 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.01g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 5mL, 5g/L4In aqueous solution, lucifuge stands 0.5h, then is placed on the high voltage mercury lamp radiation 4h of optical wavelength 365nm; After reaction terminates, take out product and be washed to neutrality, drying 3h, obtain Au/TiO for 180 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 0.01g, and lucifuge stands 120min; After illumination 160min, the cinnamic degradation rate of gaseous state is up to 87.3%.
Embodiment 4
(1) 2g carbon fiber paper is joined the dense HNO of 80mL3With dense H2SO4In the nitration mixture that (volume ratio is 1:2) forms, 92 DEG C of backflow 60min, it is washed to neutrality, dries 8h, obtain the carbon fiber paper after purification for 80 DEG C, standby;
(2) 1.4g butyl titanate adds in 40mL ethanol, and stirring 3min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 0.6g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 100 DEG C dry 25min; Such moistening drying course is repeatedly performed 2 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 2.0gNaOH, 0.2gD25 titania powder adds in 12mL deionized water, and ultrasonic disperse 10min obtains the mixing suspension of NaOH and titanium dioxide;
(5) the butyl titanate solution-wet of 0.6g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 120 DEG C of hydro-thermal reaction 35h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 3h, obtain TiO for 180 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.1g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 15mL, 6g/L4In aqueous solution, lucifuge stands 2h, then is placed on the high voltage mercury lamp radiation 1h of optical wavelength 365nm; After reaction terminates, take out product and be washed to neutrality, drying 20h, obtain Au/TiO for 50 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 0.02g, and lucifuge stands 800min; After illumination 120min, the cinnamic degradation rate of gaseous state is up to 81.6%.
Embodiment 5
(1) 3g carbon fiber paper is joined 120mL, dense HNO3With dense H2SO4In the nitration mixture that (volume ratio is 1:2.5) forms, 85 DEG C of backflow 100min, it is washed to neutrality, dries 9h, obtain the carbon fiber paper after purification for 90 DEG C, standby;
(2) 2.1g butyl titanate adds in 60mL ethanol, and stirring 8min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 0.35g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 120 DEG C dry 15min; Such moistening drying course is repeatedly performed 4 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 3.5gNaOH, 0.35gD25 titania powder adds in 40mL deionized water, and ultrasonic disperse 3min obtains the mixing suspension of NaOH and titanium dioxide;
(5) the butyl titanate solution-wet of 0.35g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 100 DEG C of hydro-thermal reaction 40h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 14h, obtain TiO for 130 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.35g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 20mL, 8g/L4In aqueous solution, lucifuge stands 1.5h, then is placed on the high voltage mercury lamp radiation 2.5h of optical wavelength 365nm; After reaction terminates, take out product and be washed to neutrality, drying 5h, obtain Au/TiO for 150 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 0.35g, and lucifuge stands 510min; After illumination 180min, the cinnamic degradation rate of gaseous state is up to 90.1%.
Embodiment 6
(1) 6g carbon fiber paper is joined 150mL, dense HNO3With dense H2SO4In the nitration mixture that (volume ratio is 1:1.5) forms, 75 DEG C of backflow 170min, it is washed to neutrality, dries 4h, obtain the carbon fiber paper after purification for 140 DEG C, standby;
(2) 4.0g butyl titanate adds in 80mL ethanol, and stirring 5min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 0.45g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 150 DEG C dry 18min; Such moistening drying course is repeatedly performed 3 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 3.0gNaOH, 0.3gD25 titania powder adds in 30mL deionized water, and ultrasonic disperse 30min obtains the mixing suspension of NaOH and titanium dioxide;
(5) the butyl titanate solution-wet of 0.45g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 140 DEG C of hydro-thermal reaction 30h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 5h, obtain TiO for 110 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.45g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 16mL, 9g/L4In aqueous solution, lucifuge stands 3h, then is placed on the high voltage mercury lamp radiation 3h of optical wavelength 365nm. After reaction terminates, take out product and be washed to neutrality, drying 10h, obtain Au/TiO for 100 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 0.45g, and lucifuge stands as 600min; After illumination 180min, the cinnamic degradation rate of gaseous state is up to 91.3%.
Embodiment 7
(1) 0.8g carbon fiber paper is joined 30mL, dense HNO3With dense H2SO4In the nitration mixture that (volume ratio is 1:4) forms, 86 DEG C of backflow 50min, it is washed to neutrality, dries 11h, obtain the carbon fiber paper after purification for 70 DEG C, standby;
(2) 0.06g butyl titanate adds in 30mL ethanol, and stirring 6min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 0.06g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 90 DEG C dry 28min; Such moistening drying course is repeatedly performed 5 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 0.8gNaOH, 0.08gD25 titania powder adds in 15mL deionized water, and ultrasonic disperse 2min obtains the mixing suspension of NaOH and titanium dioxide;
(5) the butyl titanate solution-wet of 0.06g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 90 DEG C of hydro-thermal reaction 42h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 20h, obtain TiO for 70 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.06g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 8mL, 8g/L4In aqueous solution, lucifuge stands 1.2h, then is placed on the high voltage mercury lamp radiation 2.2h of optical wavelength 365nm; After reaction terminates, take out product and be washed to neutrality, drying 18h, obtain Au/TiO for 70 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 0.06g, and lucifuge stands 210min; After illumination 180min, the cinnamic degradation rate of gaseous state is up to 89.3%.
Embodiment 8
(1) 8g carbon fiber paper is joined 180mL, dense HNO3With dense H2SO4In the nitration mixture that (volume ratio is 1:3.5) forms, 87 DEG C of backflow 160min, it is washed to neutrality, dries 7h, obtain the carbon fiber paper after purification for 95 DEG C, standby;
(2) 4.8g butyl titanate adds in 180mL ethanol, and stirring 7min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 0.48g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 110 DEG C dry 16min; Such moistening drying course is repeatedly performed 5 times, obtains butyl titanate solution-wet dried carbon fiber paper;
(4) 4.8gNaOH, 0.4gD25 titania powder adds in 90mL deionized water, and ultrasonic disperse 25min obtains the mixing suspension of NaOH and titanium dioxide;
(5) then the butyl titanate solution-wet of 0.48g step (3) gained dried carbon fiber paper are added the mixing suspension of step (4) gained, and load in polytetrafluoroethyltank tank, 125 DEG C of hydro-thermal reaction 25h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 18h, obtain TiO for 90 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.48g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 30mL, 12g/L4In aqueous solution, lucifuge stands 2.5h, then is placed on the high voltage mercury lamp radiation 1.5h of optical wavelength 365nm; After reaction terminates, take out product and be washed to neutrality, drying 15h, obtain Au/TiO for 90 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 0.48g, and lucifuge stands 300min; After illumination 180min, the cinnamic degradation rate of gaseous state is up to 88.3%.
Embodiment 9
(1) 5g carbon fiber paper is joined 100mL, dense HNO3With dense H2SO4In the nitration mixture that (volume ratio is 1:1.2) forms, 93 DEG C of backflow 110min, it is washed to neutrality, dries 5h, obtain the carbon fiber paper after purification for 100 DEG C, standby;
(2) 0.25g butyl titanate adds in 50mL ethanol, and stirring 4min obtains the settled solution of butyl titanate;
(3) carbon fiber paper after the 0.25g purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, 160 DEG C dry 11min; Such moistening drying course is repeatedly performed 5 times;
(4) 2.5gNaOH, 0.25gD25 titania powder adds in 50mL deionized water, and ultrasonic disperse 4min obtains the mixing suspension of NaOH and titanium dioxide;
(5) then the butyl titanate solution-wet of 0.25g step (3) gained dried carbon fiber paper are added the mixed solution of step (4) gained, and load in polytetrafluoroethyltank tank, 115 DEG C of hydro-thermal reaction 20h, after solution cooling in polytetrafluoroethyltank tank, take out the carbon fiber paper with white depositions and be washed to neutrality, dry 15h, obtain TiO for 100 DEG C2/ CFP binary composite photo-catalyst;
(6) by the TiO of 0.25g step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl of 25mL, 7g/L4In aqueous solution, lucifuge stands 3.5h, then is placed on the high voltage mercury lamp radiation 3.5h of optical wavelength 365nm.After reaction terminates, take out product and be washed to neutrality, drying 22h, obtain Au/TiO for 105 DEG C2/ CFP tri compound nano-photocatalyst.
Catalyst activity test (with embodiment 1): wherein, Au/TiO2/ CFP tri compound nano-photocatalyst consumption is 0.25g, and lucifuge time of repose is 420min; After illumination 180min, the cinnamic degradation rate of gaseous state is up to 90.5%.
Effect example
(1) XRD detection: the Au/TiO that embodiment 1 is prepared2/ CFP tri compound nano-photocatalyst has carried out XRD analysis, and profiling results is as shown in Figure 1. As seen from Figure 1, prepared Au/TiO2The XRD figure spectrum of/CFP tri compound nano-photocatalyst occurs in that typical TiO simultaneously2The characteristic peak of anatase, elemental gold and graphitic carbon. This can predict that prepared photocatalyst has certain visible light catalysis activity.
(2) SEM and TEM detection: Fig. 2 is the SEM figure of carbon fiber paper, it can be seen that carbon fiber paper is interlocked by micron order carbon fiber and assembles. Fig. 3 and Fig. 4 is the TiO that embodiment 1 prepares2/ CFP binary composite photo-catalyst and Au/TiO2SEM figure, the TiO as seen from the figure of/CFP tri compound nano-photocatalyst2Nano wire uniformly and completely covers the surface of carbon fiber, it was shown that TiO2Compound between nano wire with carbon fiber not simply mixes. By tem analysis (Fig. 5), it can be observed that Au/TiO2Nano level Au granule in/CFP tri compound nano-photocatalyst.
(3)Au/TiO2/ CFP tri compound nano-photocatalyst is to the cinnamic visible light photocatalytic degradation research of gas phase: Fig. 6 is the Au/TiO that embodiment 1 prepares2/ CFP tri compound nano-photocatalyst is to cinnamic adsorption curve and kinetics of photocatalytic degradation curve. As seen from the figure, this photocatalyst shows good absorption and photocatalytic activity, and degradation results shows, at 180min, cinnamic degradation rate to be reached 90.7%.
The Au/TiO that the embodiment of the present invention 1��9 prepares2In/CFP tri compound nano-photocatalyst, diameter be 5��10 microns carbon fiber surface by diameter be 20��60 nanometers, fully wrapped around up to the titanium dioxide nano thread of a few micrometers, and the gold nano grain having particle size to be 2��10 nanometers is dispersed in the surface of carbon fiber and titanium dioxide nano thread; Its X-ray diffraction spectra, laser Raman spectroscopy and x-ray photoelectron power spectrum show that three kinds of elements of C, Ti and Au coexist in catalyst. UV-Vis DRS spectrum then shows that this tri compound nano-photocatalyst has superior Uv and visible light absorbent properties. Au/TiO prepared by the present invention is can be seen that by result above2/ CFP tri compound nano-photocatalyst is the new material of a kind of high absorption and visible light catalysis activity.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. an Au/TiO2The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that comprise the steps of:
(1) carbon fiber paper is immersed in dense HNO3With dense H2SO4In the nitration mixture of composition, reflux 30��180min at 85��95 DEG C, is washed out to neutrality, by the drying precipitate after washing, obtains the carbon fiber paper after purification;
(2) butyl titanate is joined in ethanol, after stirring, obtain the settled solution of the butyl titanate that concentration is 2��50g/L;
(3) carbon fiber paper after the purification of step (1) gained is joined step (2) gained butyl titanate settled solution in moistening, take out, dry; Repeat moistening and dry run 2��5 times, obtain butyl titanate solution-wet dried carbon fiber paper;
(4) the mixing suspension of preparation NaOH and titanium dioxide, the wherein final concentration of 50��200g/L of NaOH, the final concentration of 4��20g/L of titanium dioxide;
(5) the butyl titanate solution-wet of step (3) gained dried carbon fiber paper are added in step (4) in the mixing suspension of gained hydro-thermal reaction 6��48h at 90��150 DEG C; Products therefrom cyclic washing, to neutral, by the drying precipitate after washing, obtains TiO2/ CFP binary composite photo-catalyst;
(6) by the TiO of step (5) gained2/ CFP binary composite photo-catalyst joins the HAuCl that concentration is 5��15g/L4In aqueous solution, lucifuge stands 0.5��5h, then is placed under ultraviolet and irradiates 1��5h; Taking out product, cyclic washing, to neutral, by the drying precipitate after washing, obtains Au/TiO2/ CFP tri compound nano-photocatalyst.
2. Au/TiO according to claim 12The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that:
Dense HNO described in step (1)3Mass fraction be 69%.
3. Au/TiO according to claim 12The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that:
Dense H described in step (1)2SO4Mass fraction be 98%.
4. Au/TiO according to claim 12The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that:
Dense HNO in nitration mixture described in step (1)3With dense H2SO4Volume ratio be 1:(1��5).
5. Au/TiO according to claim 12The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that:
Baking temperature described in step (1) is 50��180 DEG C; Drying time is 3��12h.
6. Au/TiO according to claim 12The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that:
Baking temperature described in step (3) is 50��180 DEG C, and drying time is 10��30min.
7. Au/TiO according to claim 12The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that:
Baking temperature described in step (5) is 50��180 DEG C, and drying time is 3��24h.
8. Au/TiO according to claim 12The preparation method of/CFP tri compound nano-photocatalyst, it is characterised in that:
Baking temperature described in step (6) is 50��180 DEG C, and drying time is 3��24h.
9. an Au/TiO2/ CFP tri compound nano-photocatalyst, it is characterised in that: the preparation method according to any one of claim 1��8 prepares.
10. the Au/TiO described in claim 92The application in the degraded volatile organic matter field of/CFP tri compound nano-photocatalyst.
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