CN106000389A - Photocatalyst and preparation method thereof - Google Patents
Photocatalyst and preparation method thereof Download PDFInfo
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- CN106000389A CN106000389A CN201610550449.4A CN201610550449A CN106000389A CN 106000389 A CN106000389 A CN 106000389A CN 201610550449 A CN201610550449 A CN 201610550449A CN 106000389 A CN106000389 A CN 106000389A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 180
- 238000002360 preparation method Methods 0.000 title claims abstract description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 150
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 98
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 98
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 98
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 98
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 97
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 32
- 238000000926 separation method Methods 0.000 abstract description 7
- 229910003849 O-Si Inorganic materials 0.000 abstract description 6
- 229910003872 O—Si Inorganic materials 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 8
- 239000003344 environmental pollutant Substances 0.000 abstract 2
- 231100000719 pollutant Toxicity 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- 238000013032 photocatalytic reaction Methods 0.000 abstract 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 85
- 238000007146 photocatalysis Methods 0.000 description 27
- 238000010586 diagram Methods 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/613—
-
- B01J35/633—
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a SiO2/Bi photocatalyst and a preparation method thereof. According to the SiO2/Bi photocatalyst, SiO2 is loaded on a metal Bi in situ, so that on one hand, the specific surface area of the SiO2/Bi photocatalyst is greatly increased as compared with that of a Bi photocatalyst, the high specific surface area is beneficial to adsorption of a photocatalytic material on a target pollutant, the contact area of the photocatalyst and the target pollutant is increased, and thus the photocatalytic property can be improved; on the other hand, due to adoption of SiO2, a Bi-O-Si bond can be formed in the SiO2/Bi photocatalyst; under the action of plasma, electrons on the metal Bi are rapidly transferred to the surface of the SiO2/Bi photocatalyst through the Bi-O-Si bond, so that separation and transferring of carriers are promoted, the yield of free radicals is increased, and the photocatalytic efficiency is further improved. In addition, the SiO2/Bi photocatalyst provided by the invention has the advantages of low cost and good chemical stability, and can be recycled and used for multiple times in photocatalytic reaction.
Description
Technical field
The present invention relates to photocatalysis field, particularly relate to a kind of SiO2/ Bi photocatalyst and preparation method thereof.
Background technology
Photocatalyst is a kind of under the irradiation of light, self does not changes, but can promote the material of chemical reaction.At present, light
Catalysis, as a most potential industry, has been widely used for environment remediation, clean energy resource production, the modification of carbon and chemistry
Each fields such as synthesis, are just solving the energy and problem of environmental pollution in the way of sustainable development.Photocatalyst can include semiconductor light
All multiple types such as catalyst and plasma photocatalysis agent, wherein, plasma photocatalysis agent is because of the photocatalysis performance of its excellence
Develop rapidly.
When the frequency of incident illumination is consistent with the concussion frequency of noble metal conduction band electron, noble metal will produce surface plasma altogether
Phenomenon of shaking, to improve efficiency of light absorption, promotes the separation of photo-generated carrier, thus reduces the recombination probability of photo-generated carrier, thus
Plasma photocatalysis agent has stronger photocatalysis performance compared with semiconductor light-catalyst.In plasma photocatalysis agent,
Being most widely used of the noble metals such as Au, Ag.But, the earth of noble metal stores rareness, and market value is expensive, thus greatly
Inhibit greatly its application in photocatalysis technology.
Therefore, find a kind of cheap material but with class noble metal character and become inevitable.Base metal Bi has because of it
Plasma-catalytic effect and receive much concern, but, compared with noble metal, base metal Bi as photocatalyst photocatalysis imitate
Rate is relatively low, limits the promotion and application of base metal Bi photocatalyst.
Summary of the invention
The present invention provides a kind of SiO2/ Bi photocatalyst and preparation method thereof, urges solving Bi photocatalyst light in prior art
Change inefficient technical problem.
The present invention provides a kind of SiO2The preparation method of/Bi photocatalyst, described method includes:
By Bi (NO3)3·5H2O is dissolved in the HNO of 1mol/L3In, obtain Bi (NO3)3·5H2O acid solution；
Ethylene glycol is added described Bi (NO3)3·5H2In O acid solution, after stirring 30min, add SiO2, obtain SiO2/Bi
Photocatalyst presoma, wherein, SiO2With Bi (NO3)3·5H2The mass ratio of O is 1%-10%；
By described SiO2After/Bi photocatalyst presoma carries out hydro-thermal reaction, it is centrifuged, washs, obtains SiO after drying2/ Bi light
Catalyst.
Preferably, described method also includes:
Described Bi (NO is added at ethylene glycol3)3·5H2After O acid solution, before stirring 30-60min, at described Bi (NO3)3
·5H2O acid solution adds PVP, wherein, Bi (NO3)3·5H2The mass ratio of O Yu PVP is 0.364:0.5-1.
Preferably, described SiO2With Bi (NO3)3·5H2The mass ratio of O is 3%.
Preferably, the hydrothermal temperature of described hydro-thermal reaction 120 DEG C-200 DEG C.
Preferably, the response time of described hydro-thermal reaction is 12h-48h.
Preferably, described Bi (NO3)3·5H2O and HNO3Mol ratio be 0.75:5-10.
Preferably, described HNO3It is 1:4-6 with the volume ratio of ethylene glycol.
The present invention also provides for a kind of SiO2/ Bi photocatalyst, described SiO2/ Bi photocatalyst is any according to claim 1-7
Prepared by a kind of preparation method.
The technical scheme that embodiments of the invention provide can include following beneficial effect:
The present invention provides a kind of SiO2/ Bi photocatalyst and preparation method thereof, the present invention loads SiO on metal Bi in situ2,
Prepare the novel SiO with excellent photocatalysis performance2/ Bi photocatalyst.On the one hand, SiO2The relatively Bi photocatalysis of/Bi photocatalyst
For agent, specific surface area is greatly increased, and high-specific surface area is conducive to the catalysis material absorption to target contaminant, thus increases
Photocatalyst and the contact area of target contaminant, promote that photocatalysis performance improves.On the other hand, SiO is added2After, SiO2/Bi
Forming Bi-O-Si key in photocatalyst, under action of plasma, the electronics on metal Bi passes through Bi-O-Si key fast transfer
To SiO2The surface of/Bi photocatalyst, thus promote separation and the transfer of carrier, increase the productivity of free radical, improve further
Photocatalysis efficiency.It addition, the SiO that the present invention provides2/ Bi photocatalyst also has advantage with low cost, that chemical stability is strong,
Can in light-catalyzed reaction recycled for multiple times.
It should be appreciated that it is only exemplary and explanatory that above general description and details hereinafter describe, can not
Limit the present invention.
Accompanying drawing explanation
Fig. 1 is a kind of SiO provided in the embodiment of the present invention2The flow chart of/Bi photocatalyst preparation method；
Fig. 2 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst and the XRD comparison diagram of pure Bi photocatalyst；
Fig. 3 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst and the FTIR comparison diagram of pure Bi photocatalyst；
Fig. 4 is the SiO of the embodiment of the present invention 2 preparation2The SEM figure of the amplification of/Bi photocatalyst 100,000 times；
Fig. 5 is the SiO of the embodiment of the present invention 2 preparation2The SEM figure of the amplification of/Bi photocatalyst 50,000 times；
Fig. 6 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst TEM schemes；
Fig. 7 is the SiO of the embodiment of the present invention 2 preparation2The HRTEM figure of/Bi photocatalyst；
Fig. 8 is the SiO of the embodiment of the present invention 2 preparation2The EDX figure of/Bi photocatalyst；
Fig. 9 is the SiO of the embodiment of the present invention 2 preparation2The EDX figure of/Bi photocatalyst C element；
Figure 10 is the SiO of the embodiment of the present invention 2 preparation2The EDX of/Bi photocatalyst O element schemes；
Figure 11 is the SiO of the embodiment of the present invention 2 preparation2The EDX of/Bi photocatalyst Bi element schemes；
Figure 12 is the SiO of the embodiment of the present invention 2 preparation2The EDX of/Bi photocatalyst Si element schemes；
Figure 13 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst takes off with the BET nitrogen adsorption of pure Bi photocatalyst
Attached comparison diagram；
Figure 14 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst and the pore-size distribution comparison diagram of pure Bi photocatalyst；
Figure 15 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst sputtering 25nm, SiO2/ Bi photocatalyst does not sputters
With pure SiO2XPS comparison diagram；
Figure 16 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst sputtering 25nm, SiO2/ Bi photocatalyst do not sputters,
With pure SiO2XPS partial enlargement comparison diagram corresponding to C element；
Figure 17 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst sputtering 25nm, SiO2/ Bi photocatalyst do not sputters,
With pure SiO2XPS partial enlargement comparison diagram corresponding to O element；
Figure 18 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst sputtering 25nm and SiO2/ Bi photocatalyst does not sputters
XPS partial enlargement comparison diagram corresponding to Bi element；
Figure 19 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst sputtering 25nm, SiO2/ Bi photocatalyst do not sputters,
With pure SiO2XPS partial enlargement comparison diagram corresponding to Si element；
Figure 20 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst contrasts with the UV-Vis DRS of pure Bi photocatalyst
Figure；
Figure 21 is the time resolution fluorescence spectral figure of the pure Bi photocatalyst that the present invention provides；
Figure 22 is the SiO of the embodiment of the present invention 2 preparation2The time resolution fluorescence spectral figure of/Bi photocatalyst；
Figure 23 is the SiO of the embodiment of the present invention 2 preparation2NO removed by the ultraviolet light of/Bi photocatalyst and pure Bi photocatalystx
The detection comparison diagram of superoxide radical；
Figure 24 is the SiO of the embodiment of the present invention 2 preparation2NO removed by the ultraviolet light of/Bi photocatalyst and pure Bi photocatalystx
The base detection comparison diagram of hydroxyl free；
Figure 25 is the different SiO of the embodiment of the present invention 2,3 and 4 preparation2The SiO of load capacity2The ultraviolet light of/Bi photocatalyst
Remove NOxDegradation efficiency figure；
Figure 26 is the SiO of the different hydrothermal temperatures of the embodiment of the present invention 2,5 and 6 preparation2The ultraviolet of/Bi photocatalyst
Light removes NOxDegradation efficiency figure；
Figure 27 is the SiO of the different hydro-thermal reaction times of invention embodiment 2,7 and 8 preparation2/ Bi photocatalyst
Ultraviolet light remove NOxDegradation efficiency figure；
Figure 28 is the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst, pure Bi photocatalyst and SiO2Ultraviolet light go
Except NOxDegradation efficiency figure.
Detailed description of the invention
Here will illustrate exemplary embodiment in detail, its example represents in the accompanying drawings.Explained below relates to attached
During figure, unless otherwise indicated, the same numbers in different accompanying drawings represents same or analogous key element.Following exemplary is implemented
Embodiment described in example does not represent all embodiments consistent with the present invention.On the contrary, they be only with such as
The example of the device that some aspects that described in detail in appended claims, the present invention are consistent.
Each embodiment in this specification all uses the mode gone forward one by one to describe, identical similar part between each embodiment
Seeing mutually, what each embodiment stressed is the difference with other embodiments.
Embodiment 1
Refer to Fig. 1, a kind of SiO provided is provided in the embodiment of the present invention2The flow chart of/Bi photocatalyst preparation method.
As seen from Figure 1, described SiO2The preparation method of/Bi photocatalyst comprises the following steps:
Step S101: by 0.364g Bi (NO3)3·5H2O is dissolved in the HNO of 10ml 1mol/L3In, obtain Bi (NO3)3
·5H2O acid solution；
Step S102: 55ml ethylene glycol is added described Bi (NO3)3·5H2In O acid solution, add after stirring 30min
0.011g SiO2, obtain SiO2/ Bi photocatalyst presoma；
Step S103: by described SiO2/ Bi photocatalyst presoma at 160 DEG C after hydro-thermal reaction 24h, centrifugal, washing,
Obtain SiO after drying2/ Bi photocatalyst.
Embodiment 2
55ml ethylene glycol, on the basis of embodiment 1, is being added described Bi (NO by the present embodiment3)3·5H2O acid solution it
After, it is additionally included in described Bi (NO before stirring 30min3)3·5H2O acid solution adds 0.6g PVP (Polyvinyl
Pyrrolidone, polyvinylpyrrolidone).
Test characterizes:
Refer to Fig. 2, show the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst and the XRD of pure Bi photocatalyst
(X-ray diffraction, X-ray diffraction) comparison diagram.From Figure 2 it can be seen that the SiO of embodiment 2 preparation2/ Bi photocatalyst
The corresponding angle of diffraction is 22.2 ° respectively, 26.9 °, 37.9 °, 39.6 °, 44.4 °, 45.7 °, 48.6 °, 55.8 °, 59.3 °, 62.1 °,
67.3 ° and 71.8 °, consistent with the angle of diffraction of pure Bi photocatalyst Bi, show this SiO2/ Bi photocatalyst is urged with pure Bi light
The crystal formation of agent is consistent.
Refer to Fig. 3, show the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst and the FTIR of pure Bi photocatalyst
(Fourier Transform infrared spectroscopy, fourier conversion infrared spectrum analysis instrument) comparison diagram.By Fig. 3
Visible, 466cm-1It it is the peak of Bi-O key；1095cm-1It is the vibration peak of O-Si-O, shows at SiO2/ Bi has formation
The trend of Bi-O-Si key.
Refer to Figure 4 and 5, the shown SiO being respectively the embodiment of the present invention 2 preparation2/ Bi photocatalyst amplifies 100,000 times
SEM figure and SEM (scanning electron microscope, the scanning electron microscope) figure of amplification 50,000 times.By Fig. 4
Visible with 5, the SiO of embodiment 2 preparation2/ Bi photocatalyst is by SiO2Become around Bi set of balls and particle diameter distribution is the most uniform.
Refer to Fig. 6, show the SiO of the embodiment of the present invention 2 preparation2TEM (the Transmission of/Bi photocatalyst
Electron microscope, transmission electron microscope) figure.As seen from Figure 6, the SiO of embodiment 2 preparation2/ Bi photocatalyst
In, SiO2Successfully load on Bi ball.Refer to Fig. 7, show the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalysis
HRTEM (High Resolution Transmission Electron Microscopy, the high-resolution transmission electron microscope) figure of agent.
As seen from Figure 7, the SiO of embodiment 2 preparation2SiO in/Bi photocatalyst2It is in close contact with Bi ball, shows SiO2/ Bi light
The successful structure of catalyst.
Refer to Fig. 8-12, the shown SiO being respectively the embodiment of the present invention 2 preparation2EDX (the Energy of/Bi photocatalyst
Dispersive X-Ray, energy dispersion X-ray spectrum) figure, the EDX figure of C element, the EDX figure of O element, Bi element
EDX figure and Si element EDX figure.From Fig. 8-12, the SiO of embodiment 2 preparation2In/Bi photocatalyst together
Time there is C, O, Bi and Si element, show SiO2The success of/Bi photocatalyst is combined.
Refer to Figure 13 and 14, the shown SiO being respectively the embodiment of the present invention 2 preparation2/ Bi photocatalyst is urged with pure Bi light
The BET nitrogen adsorption desorption comparison diagram of agent and pore-size distribution comparison diagram.From Figure 13 and 14, embodiment 2 preparation
SiO2The aperture of/Bi photocatalyst and specific surface area become big, the beneficially transfer of carrier, thus improve SiO2/ Bi photocatalyst
Catalytic efficiency.SiO prepared by the present embodiment2/ Bi photocatalyst and the specific surface area of pure Bi photocatalyst, pore capacities, peak pair
The diameter answered refer to table 1.
Table 1: the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst and the specific surface area of pure Bi photocatalyst, pore capacities,
The diameter that peak is corresponding.
| Sample | Specific surface area (m2/g) | Pore capacities (cm3/g) | The diameter (nm) that peak is corresponding |
| Bi photocatalyst | 16 | 0.11 | 3.7/30.1 |
| SiO2/Bi | 27 | 0.14 | 3.6/23.0 |
As can be seen from Table 1, compared with pure Bi photocatalyst, SiO2The specific surface area of/Bi photocatalyst is relatively big, due to bigger
Specific surface area be conducive to the transmission of light induced electron and the separation of photogenerated charge, thus be conducive to the photocatalysis improving photocatalyst to live
Property；It addition, specific surface area also helps greatly the attachment of target contaminant, thus improve dirt-removing power, improve photocatalysis further
The photocatalytic activity of agent.
Referring to Figure 15-19, Figure 15-19 is respectively the SiO of embodiment 2 preparation2/ Bi photocatalyst sputtering 25nm, SiO2/Bi
Photocatalyst does not sputters and pure SiO2XPS (X-ray photoelectron spectroscopy, X-ray photoelectron spectroscopic analysis)
Comparison diagram, and corresponding C element partial enlargement comparison diagram, O element partial enlargement comparison diagram, the contrast of Bi element partial enlargement
Figure, Si element partial enlargement comparison diagram.Wherein, SiO2After/Bi photocatalyst sputtering 25nm, peak value corresponding for C1s is 284.7eV；
Peak value corresponding for O1s is respectively 533.05eV, 530.8eV and 529.6eV；Peak value corresponding for Bi4f be respectively 156.8eV,
162.1eV, 158.9 and 164.2eV, peak value corresponding for Si2p is 103.8eV.Shown by Figure 15 and Figure 17, SiO2/Bi
Before photocatalyst sputtering, characteristic peak 529.6eV and 530.8eV of O1s corresponds respectively to Si-O and Bi-O, surface SiO2
Successfully load to the SiO of embodiment 2 preparation2In/Bi photocatalyst surface, and SiO2After the sputtering of/Bi photocatalyst, the spy of O1s
Levy peak 533.05eV and come from pure SiO2, show to load to SiO2The SiO of/Bi photocatalyst surface2In some is dissolved into
Inside Bi ball.Further, since the SiO after Jian She2/ Bi photocatalyst has Si2p characteristic of correspondence peak value 103.8eV, table
Bright SiO2There is Si element inside/Bi photocatalyst, prove SiO further2Prepared by the success of/Bi photocatalyst.Additionally, Bi 4f
In 156.8 and 162.1eV corresponding to zeroth order Bi, from Bi-Bi, 158.9 and 164.2eV correspond to Bi3+, from Bi-O.
Owing to the surface of Bi is easily by the dioxygen oxidation in air, therefore, SiO2The peak intensity that before the sputtering of/Bi photocatalyst, zeroth order Bi is corresponding
Little, the oxide layer that Bi surface is formed stops the further oxidation within Bi ball, the peak intensity that after sputtering, zeroth order Bi is corresponding to become big.
Refer to Figure 20, show the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst and pure Bi photocatalyst
UV-Vis DRS (UV-Vis Diffuse Reflection Spectroscopy, UV-vis DRS) comparison diagram.Can by Figure 20
See, the SiO of embodiment 2 preparation under the ultraviolet light of 280nm2/ Bi photocatalyst is basically identical with the optical absorption intensity of pure Bi,
Show this SiO2Promoting of/Bi photocatalyst photocatalytic activity mainly increases relevant with the formation of Bi-O-Si key with specific surface area.
Refer to Figure 21 and 22, the time resolution fluorescence spectral figure of the pure Bi photocatalyst that the shown present invention of being respectively provides with
And the SiO of the embodiment of the present invention 2 preparation2The time resolution fluorescence spectral figure of/Bi photocatalyst.Use light-pulse generator to pure Bi
Photocatalyst and SiO2/ Bi photocatalyst sample is irradiated, and obtains time resolution fluorescence spectral.By to time-resolved fluorescence
Collection of illustrative plates is fitted, thus obtains the fluorescence lifetime of photo-generated carrier.Fluorescence lifetime can reflect the separation efficiency of carrier, glimmering
The light life-span is the longest, and carrier separation efficiency is the highest.Can be obtained by Figure 21 and 22, the SiO of embodiment 2 preparation2/ Bi photocatalyst
Fluorescence lifetime be 8.34, the fluorescence lifetime of pure Bi photocatalyst is 7.76, SiO2/ Bi photocatalyst is compared to pure Bi photocatalysis
Agent fluorescence lifetime increases, thus the separation of beneficially carrier, and then improve SiO2The catalytic performance of/Bi photocatalyst.
Refer to Figure 23 and 24, the shown SiO being respectively the embodiment of the present invention 2 preparation2/ Bi photocatalyst is urged with pure Bi light
The ultraviolet light of agent removes the detection comparison diagram of NOx superoxide radical and the base detection contrast of ultraviolet light removal NOx hydroxyl free
Figure.From Figure 23 and 24, SiO2/ Bi photocatalyst is compared to pure Bi photocatalyst superoxide radical and hydroxyl when reaction
Free radical intensity substantially increases, beneficially SiO2The raising of/Bi photocatalyst photocatalysis performance.
Embodiment 3
SiO in the present embodiment2Addition be 0.0364g, other steps and SiO described in embodiment 22/ Bi photocatalyst
Preparation method identical.
Embodiment 4
SiO in the present embodiment2Addition be 0.364g, other steps and SiO described in embodiment 22/ Bi photocatalyst
Preparation method is identical.
Embodiment 5
SiO in the present embodiment2The temperature of/Bi photocatalyst presoma hydro-thermal reaction is 120 DEG C, other steps and embodiment 2
Described SiO2The preparation method of/Bi photocatalyst is identical.
Embodiment 6
SiO in the present embodiment2The temperature of/Bi photocatalyst presoma hydro-thermal reaction is 200 DEG C, other steps and embodiment 2
Described SiO2The preparation method of/Bi photocatalyst is identical.
Embodiment 7
SiO in the present embodiment2The time of/Bi photocatalyst presoma hydro-thermal reaction is 12h, described in other steps and embodiment 2
SiO2The preparation method of/Bi photocatalyst is identical.
Embodiment 8
SiO in the present embodiment2The time of/Bi photocatalyst presoma hydro-thermal reaction is 48h, described in other steps and embodiment 2
SiO2The preparation method of/Bi photocatalyst is identical.
Embodiment 9
In the present embodiment, the addition of PVP is 0.5g, other steps and the SiO described in embodiment 22The system of/Bi photocatalyst
Preparation Method is identical.
Embodiment 10
In the present embodiment, the addition of PVP is 1.0g, other steps and the SiO described in embodiment 22The system of/Bi photocatalyst
Preparation Method is identical.
Embodiment 11
HNO in the present embodiment3Addition be 5ml, other steps and SiO described in embodiment 22/ Bi photocatalyst
Preparation method is identical.
Embodiment 12
HNO in the present embodiment3Addition be 5ml, other steps and SiO described in embodiment 22/ Bi photocatalyst
Preparation method is identical.
Embodiment 13
HNO in the present embodiment3Addition be 8ml, other steps and SiO described in embodiment 22/ Bi photocatalyst
Preparation method is identical.
Embodiment 14
In the present embodiment, the addition of ethylene glycol is 20ml, other steps and the SiO described in embodiment 22/ Bi photocatalyst
Preparation method is identical.
Embodiment 15
In the present embodiment, the addition of ethylene glycol is 60ml, other steps and the SiO described in embodiment 22/ Bi photocatalyst
Preparation method is identical.
Photocatalysis performance is tested:
In the present invention, SiO2Addition and the temperature of hydro-thermal reaction and time be to affect SiO2/ Bi photocatalyst photocatalysis
The key factor of performance, therefore, the present invention is directed to the SiO of preparation in embodiment 2-82/ Bi photocatalyst and SiO2, pure Bi
Photocatalyst carries out photocatalysis performance test, the SiO that further prepared by the checking present invention2The catalytic performance of/Bi photocatalyst.
Photocatalysis performance test detailed process is as follows: be 60% at relative humidity, and oxygen content is in the environment of 21%, and NO flows
The initial concentration that flow set is 3.3L/min, NO be 500ppb, by 0.2g embodiment 2-8 prepare SiO2/ Bi light is urged
Agent, SiO2, pure Bi photocatalyst be carried in glass disk stand-by respectively.Photocatalysis performance is tested: light source is a 280nm
Ultraviolet tube, the glass plate being loaded with above catalyst is placed in reactor, under room temperature photocatalysis remove NO.
Refer to Figure 25, show the different SiO of the embodiment of the present invention 2,3 and 4 preparation2The SiO of load capacity2/ Bi light is urged
NO removed by the ultraviolet light of agentxDegradation efficiency figure.As seen from Figure 25, SiO2/ Bi-3% photocatalyst (embodiment 2) is right
The clearance of NO is 53.6%, SiO2/ Bi-1% photocatalyst (embodiment 3) is 48.7% to the clearance of NO；SiO2/ Bi-10%
(embodiment 4) photocatalyst is 53.3% to the clearance of NO.It follows that work as SiO2Addition quality be
Bi(NO3)3·5H2O 3% time, SiO2The degradation efficiency of/Bi photocatalyst is the highest, SiO2Addition excessive or too small all
It is unfavorable for SiO2The raising of/Bi photocatalyst for degrading efficiency.
Refer to Figure 26, show the SiO of the different hydrothermal temperatures of the embodiment of the present invention 2,5 and 6 preparation2/ Bi light
NO removed by the ultraviolet light of catalystxDegradation efficiency figure.As seen from Figure 26, SiO2/ Bi-120 DEG C of photocatalyst (embodiment 5)
Clearance to NO is 23.2%；SiO2/ Bi-200 DEG C of photocatalyst (embodiment 6) is 28.3% to the clearance of NO.By
This understands, SiO2In/Bi photocatalyst preparation process, the temperature of hydro-thermal reaction is the key factor affecting its catalytic performance, and hydro-thermal is anti-
The optimum temperature answered is 160 DEG C, and temperature is too low and too high all can cause SiO2Declining to a great extent of/Bi photocatalyst catalytic performance.
Refer to Figure 27, show the SiO of the different hydro-thermal reaction times of the embodiment of the present invention 2,7 and 8 preparation2/ Bi light
NO removed by the ultraviolet light of catalystxDegradation efficiency figure.As seen from Figure 27, SiO2/ Bi-12h photocatalyst (embodiment 7)
Clearance to NO is 32.7%；SiO2/ Bi-48h photocatalyst (embodiment 8) is 33.6% to the clearance of NO.By
This understands, SiO2In/Bi photocatalyst preparation process, the time of hydro-thermal reaction is another key factor affecting its catalytic performance, water
The Best Times of thermal response is 24h, overlong time and too short all can cause SiO2Declining to a great extent of/Bi photocatalyst catalytic performance.
Refer to Figure 28, show the SiO of the embodiment of the present invention 2 preparation2/ Bi photocatalyst, pure Bi photocatalyst and SiO2
Ultraviolet light remove NOxDegradation efficiency figure.As seen from Figure 28, pure Bi photocatalyst and SiO2The clearance of NO is divided
It is not 36.9% and 0.12%.The present invention is by SiO2It is supported on metal Bi, the SiO prepared2The photocatalysis of/Bi photocatalyst is gone
Except the performance of NO has obvious reinforced effects relative to pure Bi photocatalyst.As can be seen here, SiO is used2Modify plasma
Photocatalyst Bi, not only significantly improves photocatalysis efficiency, significantly reduces photocatalysis cost in actual applications simultaneously, tool
There is prospect widely.
Term " includes ", " comprising " or its any other variant are intended to comprising of nonexcludability, so that
Process, method, article or equipment including a series of key elements not only include those key elements, but also include the most clearly
Other key elements listed, or also include the key element intrinsic for this process, method, article or equipment.Do not having
In the case of having more restriction, statement " including ... " key element limited, it is not excluded that including described key element
Process, method, article or equipment in there is also other identical element.
The above is only the detailed description of the invention of the present invention, makes to skilled artisans appreciate that or realize the present invention.
Multiple amendment to these embodiments will be apparent to one skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, this
The bright the embodiments shown herein that is not intended to be limited to, and be to fit to and principles disclosed herein and features of novelty
The widest consistent scope.
Claims (8)
1. a SiO2The preparation method of/Bi photocatalyst, it is characterised in that described method includes:
By Bi (NO3)3·5H2O is dissolved in the HNO of 1mol/L3In, obtain Bi (NO3)3·5H2O acid solution；
Ethylene glycol is added described Bi (NO3)3·5H2In O acid solution, after stirring 30min, add SiO2, obtain SiO2/Bi
Photocatalyst presoma, wherein, SiO2With Bi (NO3)3·5H2The mass ratio of O is 1%-10%；
By described SiO2After/Bi photocatalyst presoma carries out hydro-thermal reaction, it is centrifuged, washs, obtains SiO after drying2/ Bi light
Catalyst.
SiO the most according to claim 12The preparation method of/Bi photocatalyst, it is characterised in that described method is also wrapped
Include:
Described Bi (NO is added at ethylene glycol3)3·5H2After O acid solution, before stirring 30-60min, at described Bi (NO3)3
·5H2O acid solution adds PVP, wherein, Bi (NO3)3·5H2The mass ratio of O Yu PVP is 0.364:0.5-1.
SiO the most according to claim 12The preparation method of/Bi photocatalyst, it is characterised in that described SiO2With
Bi(NO3)3·5H2The mass ratio of O is 3%.
SiO the most according to claim 12The preparation method of/Bi photocatalyst, it is characterised in that described hydro-thermal reaction
Hydrothermal temperature 120 DEG C-200 DEG C.
SiO the most according to claim 12The preparation method of/Bi photocatalyst, it is characterised in that described hydro-thermal reaction
Response time be 12h-48h.
SiO the most according to claim 12The preparation method of/Bi photocatalyst, it is characterised in that described Bi (NO3)3
·5H2O and HNO3Mol ratio be 0.75:5-10.
SiO the most according to claim 12The preparation method of/Bi photocatalyst, it is characterised in that described HNO3With
The volume ratio of ethylene glycol is 1:4-6.
8. a SiO2/ Bi photocatalyst, it is characterised in that described SiO2/ Bi photocatalyst is to appoint according to claim 1-7
Anticipate prepared by a kind of preparation method.
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| CN103350226A (en) * | 2013-07-16 | 2013-10-16 | 合肥工业大学 | SiO2/Ag composite micron sphere and preparation method thereof |
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| CN103350226A (en) * | 2013-07-16 | 2013-10-16 | 合肥工业大学 | SiO2/Ag composite micron sphere and preparation method thereof |
| CN104390950A (en) * | 2014-11-03 | 2015-03-04 | 华东理工大学 | High-efficiency photocatalytic renewable SERS (surface enhanced raman scattering) substrate based on mesoporous load Ag nanowire |
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