CN106000389B - A kind of photochemical catalyst and preparation method thereof - Google Patents
A kind of photochemical catalyst and preparation method thereof Download PDFInfo
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- CN106000389B CN106000389B CN201610550449.4A CN201610550449A CN106000389B CN 106000389 B CN106000389 B CN 106000389B CN 201610550449 A CN201610550449 A CN 201610550449A CN 106000389 B CN106000389 B CN 106000389B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 87
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 87
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 87
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 87
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 86
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- -1 wherein Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 27
- 238000007146 photocatalysis Methods 0.000 abstract description 25
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000000356 contaminant Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
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- 238000012546 transfer Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 89
- 238000010586 diagram Methods 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
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- 229910000510 noble metal Inorganic materials 0.000 description 6
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 238000004544 sputter deposition Methods 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
- 229910003849 O-Si Inorganic materials 0.000 description 4
- 229910003872 O—Si Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008859 change 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
- 230000003321 amplification Effects 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 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
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 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
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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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—
Abstract
The present invention provides a kind of SiO2/ Bi photochemical catalysts and preparation method thereof, the present invention load SiO in situ on metal Bi2, on the one hand, SiO2For/Bi photochemical catalysts are compared with Bi photochemical catalysts, specific surface area greatly increases, and high-specific surface area is conducive to absorption of the catalysis material to target contaminant, so as to increase the contact area of photochemical catalyst and target contaminant, photocatalysis performance is promoted to improve.On the other hand, SiO is added in2Afterwards, SiO2Bi O Si keys are formed in/Bi photochemical catalysts, under action of plasma, the electronics on metal Bi is quickly transferred to SiO by Bi O Si keys2/ Bi photocatalyst surfaces so as to promote the separation of carrier and transfer, increase the yield of free radical, further improve photocatalysis efficiency.In addition, SiO provided by the invention2/ Bi photochemical catalysts also have the advantages that of low cost, chemical stability is strong, can in light-catalyzed reaction recycled for multiple times.
Description
Technical field
The present invention relates to photocatalysis field more particularly to a kind of SiO2/ Bi photochemical catalysts and preparation method thereof.
Background technology
Photochemical catalyst is a kind of under the irradiation of light, itself does not change, and can but promote the substance of chemical reaction.Mesh
Before, photocatalysis has been widely used for environment remediation, clean energy resource production, the modification of carbon as a most potential industry
With each field such as chemical synthesis, the energy and problem of environmental pollution are just solved in a manner of sustainable development.Photochemical catalyst may include
All multiple types such as semiconductor light-catalyst and plasma photocatalysis agent, wherein, plasma photocatalysis agent is because of its excellent light
Catalytic performance and rapidly develop.
When the frequency of incident light is consistent with the concussion frequency of noble metal conduction band electron, noble metal will generate surface etc. from
Daughter covibration improves efficiency of light absorption, promotes the separation of photo-generated carrier, so as to reduce the compound several of photo-generated carrier
Rate, thus plasma photocatalysis agent has stronger photocatalysis performance compared with semiconductor light-catalyst.Plasma light is urged
In agent, the noble metals such as Au, Ag are most widely used.However, the earth storage of noble metal is rare, market value is expensive, because
And greatly suppress its application in photocatalysis technology.
Therefore, finding a kind of cheap but substance with class noble metal property becomes inevitable.Base metal Bi is because of it
It is concerned with plasma-catalytic effect, however, compared with noble metal, base metal Bi is urged as the light of photochemical catalyst
Change less efficient, limit the promotion and application of base metal Bi photochemical catalysts.
The content of the invention
The present invention provides a kind of SiO2/ Bi photochemical catalysts and preparation method thereof, to solve Bi photochemical catalysts in the prior art
The technical issues of photocatalysis efficiency is relatively low.
The present invention provides a kind of SiO2The preparation method of/Bi photochemical catalysts, the described method includes：
By Bi (NO3)3·5H2O is dissolved in the HNO of 1mol/L3In, obtain Bi (NO3)3·5H2O acid solutions；
Ethylene glycol is added in into the Bi (NO3)3·5H2In O acid solutions, SiO is added in after stirring 30min2, obtain SiO2/Bi
Photochemical catalyst presoma, wherein, SiO2With Bi (NO3)3·5H2The mass ratio of O is 1%-10%；
By the SiO2After/Bi photochemical catalysts presoma carries out hydro-thermal reaction, SiO is obtained after centrifugation, washing, drying2/Bi
Photochemical catalyst.
Preferably, the method further includes：
Bi (the NO are added in ethylene glycol3)3·5H2After O acid solutions, before stirring 30-60min, in the Bi
(NO3)3·5H2O acid solutions add in PVP, wherein, Bi (NO3)3·5H2The mass ratio of O and PVP is 0.364:0.5-1.
Preferably, the SiO2With Bi (NO3)3·5H2The mass ratio of O is 3%.
Preferably, 120 DEG C -200 DEG C of the hydrothermal temperature of the hydro-thermal reaction.
Preferably, the reaction time of the hydro-thermal reaction is 12h-48h.
Preferably, the Bi (NO3)3·5H2O and HNO3Molar ratio be 0.75:5-10.
Preferably, the HNO3Volume ratio with ethylene glycol is 1:4-6.
The present invention also provides a kind of SiO2/ Bi photochemical catalysts, the SiO2/ Bi photochemical catalysts are appointed according to claim 1-7
Anticipate prepared by a kind of preparation method.
The technical solution that the embodiment of the present invention provides can include the following benefits：
The present invention provides a kind of SiO2/ Bi photochemical catalysts and preparation method thereof, the present invention load in situ on metal Bi
SiO2, the new SiO with excellent photocatalysis performance is made2/ Bi photochemical catalysts.On the one hand, SiO2/ Bi photochemical catalysts are compared with Bi light
For catalyst, specific surface area greatly increases, and high-specific surface area is conducive to absorption of the catalysis material to target contaminant, so as to
Increase the contact area of photochemical catalyst and target contaminant, photocatalysis performance is promoted to improve.On the other hand, SiO is added in2Afterwards,
SiO2Bi-O-Si keys are formed in/Bi photochemical catalysts, under action of plasma, the electronics on metal Bi is fast by Bi-O-Si keys
Speed is transferred to SiO2The surface of/Bi photochemical catalysts so as to promote the separation of carrier and transfer, increases the yield of free radical, into
One step improves photocatalysis efficiency.In addition, SiO provided by the invention2/ Bi photochemical catalysts also have of low cost, chemical stability
The advantages of strong, can in light-catalyzed reaction recycled for multiple times.
It should be appreciated that above general description and following detailed description are only exemplary and explanatory, not
It can the limitation present invention.
Description of the drawings
Fig. 1 is a kind of SiO provided in the embodiment of the present invention2The flow chart of/Bi photochemical catalyst preparation methods；
Fig. 2 is SiO prepared by the embodiment of the present invention 22The XRD comparison diagrams of/Bi photochemical catalysts and pure Bi photochemical catalysts；
Fig. 3 is SiO prepared by the embodiment of the present invention 22The FTIR comparison diagrams of/Bi photochemical catalysts and pure Bi photochemical catalysts；
Fig. 4 is SiO prepared by the embodiment of the present invention 22The SEM figures of 100,000 times of the amplification of/Bi photochemical catalysts；
Fig. 5 is SiO prepared by the embodiment of the present invention 22The SEM figures of 50,000 times of the amplification of/Bi photochemical catalysts；
Fig. 6 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts TEM schemes；
Fig. 7 is SiO prepared by the embodiment of the present invention 22The HRTEM figures of/Bi photochemical catalysts；
Fig. 8 is SiO prepared by the embodiment of the present invention 22The EDX figures of/Bi photochemical catalysts；
Fig. 9 is SiO prepared by the embodiment of the present invention 22The EDX figures of/Bi photochemical catalyst C elements；
Figure 10 is SiO prepared by the embodiment of the present invention 22Scheme in the EDX of/Bi photochemical catalyst O elements；
Figure 11 is SiO prepared by the embodiment of the present invention 22Scheme in the EDX of/Bi photochemical catalyst Bi elements；
Figure 12 is SiO prepared by the embodiment of the present invention 22Scheme in the EDX of/Bi photochemical catalyst Si elements；
Figure 13 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts and the BET nitrogen adsorptions of pure Bi photochemical catalysts take off
Attached comparison diagram；
Figure 14 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts and the pore-size distribution of pure Bi photochemical catalysts compare
Figure；
Figure 15 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts sputter 25nm, SiO2/ Bi photochemical catalysts do not sputter
With pure SiO2XPS comparison diagrams；
Figure 16 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts sputter 25nm, SiO2/ Bi photochemical catalysts do not splash
Penetrate, with pure SiO2The corresponding XPS partial enlargements comparison diagram of C element；
Figure 17 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts sputter 25nm, SiO2/ Bi photochemical catalysts do not splash
Penetrate, with pure SiO2The corresponding XPS partial enlargements comparison diagram of O elements；
Figure 18 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts sputter 25nm and SiO2/ Bi photochemical catalysts do not splash
The corresponding XPS partial enlargements comparison diagram of Bi elements penetrated；
Figure 19 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts sputter 25nm, SiO2/ Bi photochemical catalysts do not splash
Penetrate, with pure SiO2The corresponding XPS partial enlargements comparison diagram of Si elements；
Figure 20 is SiO prepared by the embodiment of the present invention 22The UV-Vis DRS couple of/Bi photochemical catalysts and pure Bi photochemical catalysts
Than figure；
Figure 21 is the time resolution fluorescence spectral figure of pure Bi photochemical catalysts provided by the invention；
Figure 22 is SiO prepared by the embodiment of the present invention 22The time resolution fluorescence spectral figure of/Bi photochemical catalysts；
Figure 23 is SiO prepared by the embodiment of the present invention 22The ultraviolet light removal NO of/Bi photochemical catalysts and pure Bi photochemical catalystsx
The detection comparison diagram of superoxide radical；
Figure 24 is SiO prepared by the embodiment of the present invention 22The ultraviolet light removal NO of/Bi photochemical catalysts and pure Bi photochemical catalystsx
The base detection comparison diagram of hydroxyl free；
Figure 25 is different SiO prepared by the embodiment of the present invention 2,3 and 42The SiO of load capacity2The ultraviolet light of/Bi photochemical catalysts
Remove NOxDegradation efficiency figure；
Figure 26 is the SiO of different hydrothermal temperatures prepared by the embodiment of the present invention 2,5 and 62/ Bi photochemical catalysts it is ultraviolet
Light removes NOxDegradation efficiency figure；
Figure 27 is the SiO of different the hydro-thermal reaction times prepared by invention embodiment 2,7 and 82/ Bi photochemical catalysts
Ultraviolet light removal NOxDegradation efficiency figure；
Figure 28 is SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts, pure Bi photochemical catalysts and SiO2Ultraviolet light go
Except NOxDegradation efficiency figure.
Specific embodiment
Here exemplary embodiment will be illustrated in detail, example is illustrated in the accompanying drawings.Following description is related to
During attached drawing, unless otherwise indicated, the same numbers in different attached drawings represent the same or similar element.Following exemplary embodiment
Described in embodiment do not represent and the consistent all embodiments of the present invention.On the contrary, they be only with it is such as appended
The example of the consistent device of some aspects being described in detail in claims, of the invention.
Each embodiment in this specification is described by the way of progressive, identical similar portion between each embodiment
Point just to refer each other, and the highlights of each of the examples are the differences with other embodiments.
Embodiment 1
Fig. 1 is referred to, a kind of SiO provided in the embodiment of the present invention is provided2The flow of/Bi photochemical catalyst preparation methods
Figure.
As seen from Figure 1, the SiO2The preparation method of/Bi photochemical catalysts 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 solutions；
Step S102：55ml ethylene glycol is added in into the Bi (NO3)3·5H2In O acid solutions, added in after stirring 30min
0.011g SiO2, obtain SiO2/ Bi photochemical catalyst presomas；
Step S103：By the SiO2/ Bi photochemical catalysts presoma at 160 DEG C hydro-thermal reaction for 24 hours after, centrifugation, washing,
SiO is obtained after drying2/ Bi photochemical catalysts.
Embodiment 2
55ml ethylene glycol is being added in the Bi (NO by the present embodiment on the basis of embodiment 13)3·5H2O acid solutions it
Afterwards, the Bi (NO are additionally included in before stirring 30min3)3·5H20.6g PVP (Polyvinyl are added in O acid solutions
Pyrrolidone, polyvinylpyrrolidone).
Experiment characterization：
Fig. 2 is referred to, show the SiO of the preparation of the embodiment of the present invention 22The XRD of/Bi photochemical catalysts and pure Bi photochemical catalysts
(X-ray diffraction, X-ray diffraction) comparison diagram.From Figure 2 it can be seen that SiO prepared by embodiment 22/ Bi photochemical catalysts pair
The angle of diffraction answered is 22.2 ° respectively, 26.9 °, 37.9 °, 39.6 °, 44.4 °, 45.7 °, 48.6 °, 55.8 °, 59.3 °, 62.1 °,
It is 67.3 ° and 71.8 °, consistent with the angle of diffraction of pure Bi photochemical catalysts Bi, show this SiO2/ Bi photochemical catalysts and pure Bi photocatalysis
The crystal form of agent is consistent.
Fig. 3 is referred to, show the SiO of the preparation of the embodiment of the present invention 22/ Bi photochemical catalysts and pure Bi photochemical catalysts
FTIR (Fourier Transform infrared spectroscopy, fourier conversion infrared spectrum analysis instrument) comparison diagram.
As seen from Figure 3,466cm-1It is the peak of Bi-O keys；1095cm-1It is the vibration peak of O-Si-O, shows in SiO2Bi- is formed in/Bi
The trend of O-Si keys.
Figure 4 and 5 are referred to, shown is respectively SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts amplify 100,000 times
SEM schemes and SEM (scanning electron microscope, scanning electron microscope) figure of 50,000 times of amplification.By Figure 4 and 5
As it can be seen that SiO prepared by embodiment 22/ Bi photochemical catalysts are by SiO2It is formed around Bi balls and particle diameter distribution is more uniform.
Fig. 6 is referred to, show the SiO of the preparation of the embodiment of the present invention 22TEM (the Transmission of/Bi photochemical catalysts
Electron microscope, transmission electron microscope) figure.As seen from Figure 6, the SiO that prepared by embodiment 22/ Bi photochemical catalysts
In, SiO2It successfully loads on Bi balls.Fig. 7 is referred to, show the SiO of the preparation of the embodiment of the present invention 22/ Bi photochemical catalysts
HRTEM (High Resolution Transmission Electron Microscopy, high-resolution transmission electron microscope) figure.
As seen from Figure 7, the SiO that prepared by embodiment 22SiO in/Bi photochemical catalysts2It is in close contact with Bi balls, shows SiO2/ Bi photochemical catalysts
Successful structure.
Fig. 8-12 are referred to, shown is respectively SiO prepared by the embodiment of the present invention 22EDX (the Energy of/Bi photochemical catalysts
Dispersive X-Ray, energy dispersion X-ray spectrum) figure, C element EDX figure, O elements EDX figure, Bi elements EDX figure
And the EDX figures of Si elements.By Fig. 8-12 as it can be seen that SiO prepared by embodiment 22Existed simultaneously in/Bi photochemical catalysts C, O, Bi and
Si elements, show SiO2The success of/Bi photochemical catalysts is compound.
Figure 13 and 14 is referred to, shown is respectively SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts are urged with pure Bi light
The BET nitrogen adsorptions desorption comparison diagram and pore-size distribution comparison diagram of agent.By Figure 13 and 14 as it can be seen that SiO prepared by embodiment 22/
The aperture of Bi photochemical catalysts and specific surface area become larger, and are conducive to the transfer of carrier, so as to improve SiO2/ Bi photochemical catalysts are urged
Change efficiency.SiO manufactured in the present embodiment2/ Bi photochemical catalysts are corresponding with the specific surface area, pore capacities, peak of pure Bi photochemical catalysts
Diameter refer to table 1.
Table 1：SiO prepared by the embodiment of the present invention 22The specific surface area of/Bi photochemical catalysts and pure Bi photochemical catalysts, pore volume
Amount, the corresponding diameter in peak.
| Sample | Specific surface area (m2/g) | Pore capacities (cm3/g) | The corresponding diameter in peak (nm) |
| Bi photochemical catalysts | 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 photochemical catalysts, SiO2The specific surface area of/Bi photochemical catalysts is larger, due to compared with
Big specific surface area is conducive to the transmission of light induced electron and the separation of photogenerated charge, so as to which the light for being conducive to improve photochemical catalyst is urged
Change activity；In addition, large specific surface area also helps the attachment of target contaminant, so as to improve dirt-removing power, light is further improved
The photocatalytic activity of catalyst.
Figure 15-19 is referred to, Figure 15-19 is respectively SiO prepared by embodiment 22/ Bi photochemical catalysts sputter 25nm, SiO2/
Bi photochemical catalysts do not sputter and pure SiO2XPS (X-ray photoelectron spectroscopy, x-ray photoelectron energy
Spectrum analysis) comparison diagram and corresponding C element partial enlargement comparison diagram, O element partial enlargements comparison diagram, Bi elements locally put
Big comparison diagram, Si element partial enlargement comparison diagrams.Wherein, SiO2The corresponding peak values of C1s are after/Bi photochemical catalysts sputtering 25nm
284.7eV；The corresponding peak values of O1s are respectively 533.05eV, 530.8eV and 529.6eV；The corresponding peak values of Bi4f are respectively
156.8eV, 162.1eV, 158.9 and the corresponding peak value of 164.2eV, Si2p are 103.8eV.SiO is shown by Figure 15 and Figure 172/
Before the sputtering of Bi photochemical catalysts, the characteristic peak 529.6eV and 530.8eV of O1s correspond respectively to Si-O and Bi-O, surface SiO2Success
Load to the SiO of the preparation of embodiment 22In/Bi photocatalyst surfaces, and SiO2After the sputtering of/Bi photochemical catalysts, the characteristic peak of O1s
533.05eV come from pure SiO2, show to load to SiO2The SiO of/Bi photocatalyst surfaces2In some be dissolved into Bi balls
Portion.Further, since the SiO after sputtering2In/Bi photochemical catalysts there is the corresponding characteristic peaks 103.8eV of Si2p, show SiO2/Bi
There are Si elements inside photochemical catalyst, SiO is further proved2The successful preparation of/Bi photochemical catalysts.In addition, 156.8 in Bi 4f
Correspond to zeroth order Bi with 162.1eV, correspond to Bi from Bi-Bi, 158.9 and 164.2eV3+, from Bi-O.Due to the surface of Bi
Easily by the dioxygen oxidation in air, therefore, SiO2The corresponding peak intensities of zeroth order Bi are small before the sputtering of/Bi photochemical catalysts, Bi surfaces shape
Into oxide layer prevent Bi balls inside further oxidation, the corresponding peak intensities of zeroth order Bi become larger after sputtering.
Figure 20 is referred to, show the SiO of the preparation of the embodiment of the present invention 22/ Bi photochemical catalysts and pure Bi photochemical catalysts
UV-Vis DRS (UV-Vis Diffuse Reflection Spectroscopy, UV-vis DRS) comparison diagram.By scheming
20 as it can be seen that the SiO that under the ultraviolet light of 280nm prepared by embodiment 22The optical absorption intensity basic one of/Bi photochemical catalysts and pure Bi
It causes, shows this SiO2The formation that the promotion of/Bi photochemical catalyst photocatalytic activities mainly increases with specific surface area with Bi-O-Si keys has
It closes.
Figure 21 and 22 are referred to, shown is respectively the time resolution fluorescence spectral figure of pure Bi photochemical catalysts provided by the invention
And SiO prepared by the embodiment of the present invention 22The time resolution fluorescence spectral figure of/Bi photochemical catalysts.Using light-pulse generator to pure Bi
Photochemical catalyst and SiO2/ Bi photochemical catalyst samples are irradiated, and obtain time resolution fluorescence spectral.By glimmering to time resolution
Light collection of illustrative plates is fitted, so as to obtain the fluorescence lifetime of photo-generated carrier.Fluorescence lifetime can reflect the separative efficiency of carrier,
Fluorescence lifetime is longer, and carrier separation efficiency is higher.It can be obtained by Figure 21 and 22, SiO prepared by embodiment 22/ Bi photochemical catalysts
Fluorescence lifetime is 8.34, and the fluorescence lifetime of pure Bi photochemical catalysts is 7.76, SiO2/ Bi photochemical catalysts are compared to pure Bi photochemical catalysts
Fluorescence lifetime increases, and so as to be conducive to the separation of carrier, and then improves SiO2The catalytic performance of/Bi photochemical catalysts.
Figure 23 and 24 are referred to, shown is respectively SiO prepared by the embodiment of the present invention 22/ Bi photochemical catalysts are urged with pure Bi light
The base detection comparison of the detection comparison diagram and ultraviolet light removal NOx hydroxyl frees of the ultraviolet light removal NOx superoxide radicals of agent
Figure.By Figure 23 and 24 as it can be seen that SiO2/ Bi photochemical catalysts compared to pure Bi photochemical catalysts reaction when superoxide radical and hydroxyl from
Substantially increased by rheobase, be conducive to SiO2The raising of/Bi photochemical catalyst photocatalysis performances.
Embodiment 3
SiO in the present embodiment2Addition for 0.0364g, other steps and the SiO described in embodiment 22/ Bi photochemical catalysts
Preparation method it is identical.
Embodiment 4
SiO in the present embodiment2Addition for 0.364g, other steps and the SiO described in embodiment 22/ Bi photochemical catalysts
Preparation method it is identical.
Embodiment 5
SiO in the present embodiment2The temperature of/Bi photochemical catalyst presoma hydro-thermal reactions is 120 DEG C, other steps and embodiment
SiO described in 22The preparation method of/Bi photochemical catalysts is identical.
Embodiment 6
SiO in the present embodiment2The temperature of/Bi photochemical catalyst presoma hydro-thermal reactions is 200 DEG C, other steps and embodiment
SiO described in 22The preparation method of/Bi photochemical catalysts is identical.
Embodiment 7
SiO in the present embodiment2The time of/Bi photochemical catalyst presoma hydro-thermal reactions is 12h, other steps and embodiment 2
The SiO2The preparation method of/Bi photochemical catalysts is identical.
Embodiment 8
SiO in the present embodiment2The time of/Bi photochemical catalyst presoma hydro-thermal reactions is 48h, other steps and embodiment 2
The SiO2The preparation method of/Bi photochemical catalysts is identical.
Embodiment 9
The addition of PVP is 0.5g, other steps and the SiO described in embodiment 2 in the present embodiment2/ Bi photochemical catalysts
Preparation method is identical.
Embodiment 10
The addition of PVP is 1.0g, other steps and the SiO described in embodiment 2 in the present embodiment2/ Bi photochemical catalysts
Preparation method is identical.
Embodiment 11
HNO in the present embodiment3Addition for 5ml, other steps and the SiO described in embodiment 22The system of/Bi photochemical catalysts
Preparation Method is identical.
Embodiment 12
HNO in the present embodiment3Addition for 5ml, other steps and the SiO described in embodiment 22The system of/Bi photochemical catalysts
Preparation Method is identical.
Embodiment 13
HNO in the present embodiment3Addition for 8ml, other steps and the SiO described in embodiment 22The system of/Bi photochemical catalysts
Preparation Method is identical.
Embodiment 14
The addition of ethylene glycol is 20ml, other steps and the SiO described in embodiment 2 in the present embodiment2/ Bi photochemical catalysts
Preparation method it is identical.
Embodiment 15
The addition of ethylene glycol is 60ml, other steps and the SiO described in embodiment 2 in the present embodiment2/ Bi photochemical catalysts
Preparation method it is identical.
Photocatalysis performance is tested：
In the present invention, SiO2Addition and hydro-thermal reaction temperature and the time be influence SiO2/ Bi photochemical catalyst light
An important factor for catalytic performance, therefore, the present invention is for the SiO prepared in embodiment 2-82/ Bi photochemical catalysts and SiO2, it is pure
Bi photochemical catalysts carry out photocatalysis performance test, the SiO that further prepared by the verification present invention2The catalytic performance of/Bi photochemical catalysts.
Photocatalysis performance test detailed process is as follows：It is 60% in relative humidity, oxygen content is NO in 21% environment
The flow set of stream is 3.3L/min, and the initial concentration of NO is 500ppb, by SiO made from 0.2g embodiments 2-82/ Bi light is urged
Agent, SiO2, pure Bi photochemical catalysts are carried in glass disk for use respectively.Photocatalysis performance is tested：Light source is a 280nm
Ultraviolet tube, by load have more than catalyst glass plate be placed in reactor, under room temperature photocatalysis remove NO.
Figure 25 is referred to, show the different SiO of the preparation of the embodiment of the present invention 2,3 and 42The SiO of load capacity2/ Bi photocatalysis
The ultraviolet light removal NO of agentxDegradation efficiency figure.As seen from Figure 25, SiO2/ Bi-3% photochemical catalysts (embodiment 2) remove NO
Except rate is 53.6%, SiO2/ Bi-1% photochemical catalysts (embodiment 3) are 48.7% to the removal rate of NO；SiO2/ Bi-10% is (real
Apply example 4) photochemical catalyst is 53.3% to the removal rate of NO.It follows that work as SiO2Addition quality be Bi (NO3)3·5H2O's
When 3%, SiO2The degradation efficiency highest of/Bi photochemical catalysts, SiO2Addition it is excessive or too small be unfavorable for SiO2/ Bi light
The raising of catalyst degradation efficiency.
Figure 26 is referred to, show the SiO of the different hydrothermal temperatures of the preparation of the embodiment of the present invention 2,5 and 62/ Bi light
The ultraviolet light removal NO of catalystxDegradation efficiency figure.As seen from Figure 26, SiO2/ Bi-120 DEG C of photochemical catalyst (embodiment 5) is right
The removal rate of NO is 23.2%；SiO2/ Bi-200 DEG C of photochemical catalyst (embodiment 6) is 28.3% to the removal rate of NO.Thus may be used
Know, SiO2The temperature of hydro-thermal reaction is hydro-thermal reaction an important factor for influencing its catalytic performance in/Bi photochemical catalyst preparation process
Optimum temperature for 160 DEG C, temperature is too low and excessively high can cause SiO2/ Bi photochemical catalyst catalytic performances decline to a great extent.
Figure 27 is referred to, show the SiO of the different the hydro-thermal reaction times of the preparation of the embodiment of the present invention 2,7 and 82/ Bi light
The ultraviolet light removal NO of catalystxDegradation efficiency figure.As seen from Figure 27, SiO2/ Bi-12h photochemical catalysts (embodiment 7) are to NO
Removal rate be 32.7%；SiO2/ Bi-48h photochemical catalysts (embodiment 8) are 33.6% to the removal rate of NO.It follows that
SiO2The time of hydro-thermal reaction is another key factor for influencing its catalytic performance in/Bi photochemical catalyst preparation process, and hydro-thermal is anti-
The Best Times answered overlong time and too short can cause SiO for for 24 hours2/ Bi photochemical catalyst catalytic performances decline to a great extent.
Figure 28 is referred to, show the SiO of the preparation of the embodiment of the present invention 22/ Bi photochemical catalysts, pure Bi photochemical catalysts and SiO2
Ultraviolet light removal NOxDegradation efficiency figure.As seen from Figure 28, pure Bi photochemical catalysts and SiO2Removal rate to NO is respectively
36.9% and 0.12%.The present invention is by SiO2It is supported on metal Bi, SiO obtained2The photocatalysis removal NO of/Bi photochemical catalysts
Performance have apparent enhancing effect compared with pure Bi photochemical catalysts.It can be seen that use SiO2To modify plasma photocatalysis
Agent Bi not only significantly improves photocatalysis efficiency, while significantly reduces the cost of photocatalysis in practical applications, has very
Extensive prospect.
Term " comprising ", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that bag
To include process, method, article or the equipment of a series of elements not only include those elements, but also including being not explicitly listed
It other element or further includes as elements inherent to such a process, method, article, or device.Do not limiting more
In the case of, the element that is limited by sentence "including a ...", it is not excluded that in the process including the element, method, object
Also there are other identical elements in product or equipment.
The above is only the specific embodiment of the present invention, is made skilled artisans appreciate that or realizing this hair
It is bright.A variety of modifications of these embodiments will be apparent to one skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide scope caused.
Claims (5)
1. a kind of SiO2The preparation method of/Bi photochemical catalysts, which is characterized in that the described method includes：
By Bi (NO3)3·5H2O is dissolved in the HNO of 1mol/L3In, obtain Bi (NO3)3·5H2O acid solutions；
Ethylene glycol is added in into the Bi (NO3)3·5H2In O acid solutions, in the Bi (NO3)3·5H2PVP is added in O acid solutions,
Wherein, Bi (NO3)3·5H2The mass ratio of O and PVP is 0.364:0.5:1；SiO is added in after stirring 30min2, obtain SiO2/ Bi light
Catalyst precursor, wherein, SiO2With Bi (NO3)3·5H2The mass ratio of O is 1%-10%；
By the SiO2/ Bi photochemical catalysts presoma carry out hydro-thermal reaction, at 160 DEG C hydro-thermal reaction for 24 hours after, centrifugation, washing,
SiO is obtained after drying2/ Bi photochemical catalysts.
2. SiO according to claim 12The preparation method of/Bi photochemical catalysts, which is characterized in that the SiO2With Bi
(NO3)3·5H2The mass ratio of O is 3%.
3. SiO according to claim 12The preparation method of/Bi photochemical catalysts, which is characterized in that the Bi (NO3)3·
5H2O and HNO3Molar ratio be 0.75:5-10.
4. SiO according to claim 12The preparation method of/Bi photochemical catalysts, which is characterized in that the HNO3With ethylene glycol
Volume ratio be 1:4-6.
5. a kind of SiO2/ Bi photochemical catalysts, which is characterized in that the SiO2/ Bi photochemical catalysts are arbitrary according to claim 1-4
Prepared by a kind of preparation method.
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