CN106622234A - Cerium oxide nanometer fiber photocatalyst loading gold nanoparticles and preparation method thereof - Google Patents
Cerium oxide nanometer fiber photocatalyst loading gold nanoparticles and preparation method thereof Download PDFInfo
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- CN106622234A CN106622234A CN201611096003.5A CN201611096003A CN106622234A CN 106622234 A CN106622234 A CN 106622234A CN 201611096003 A CN201611096003 A CN 201611096003A CN 106622234 A CN106622234 A CN 106622234A
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 39
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010931 gold Substances 0.000 title claims abstract description 31
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 title claims abstract description 11
- 238000011068 loading method Methods 0.000 title abstract description 12
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 28
- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920003082 Povidone K 90 Polymers 0.000 claims abstract description 3
- 239000002121 nanofiber Substances 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 27
- 238000009413 insulation Methods 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 229960004217 benzyl alcohol Drugs 0.000 abstract 1
- 235000019445 benzyl alcohol Nutrition 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 241000165940 Houjia Species 0.000 description 4
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 aldehyde compound Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B01J35/39—
-
- B01J35/58—
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
Abstract
The invention relates to the technical fields of nanometer material preparation and photocatalysis, and concretely discloses a cerium oxide nanometer fiber photocatalyst loading gold nanoparticles. The cerium oxide nanometer fiber photocatalyst is characterized in that the gold nanoparticles are uniformly loaded on the surface of the cerium oxide nanometer fiber; the loading quantity of the gold nanoparticles is 0.1 to 2.5 weight percent. The invention also discloses a preparation method of the photocatalyst. The method comprises the following steps of (1) preparing a spinning solvent: respectively weighing PVP (PVP-K90), cerous nitrate and chloroauric acid into DMF; performing stirring for 12 to 24 h under room temperature to form the spinning solvent; (2) transferring the spinning solvent into an injector with a 21# needle head; exerting voltage; preparing Ce(NO3)3/HAuCl4/PVP nanometer fiber; (3) performing heat treatment: raising the temperature of the Ce(NO3)3/HAuCl4/PVP nanometer fiber to 100 DEG C; performing heat preservation for 5h; then, raising the temperature to 200 DEG C; performing heat preservation for 1h; raising the temperature to 500 DEG C; performing heat preservation for 2h; finally, performing natural cooling to the room temperature; obtaining the cerium oxide nanometer fiber photocatalyst. The preparation method provided by the invention has the advantages that simplicity and controllability are realized; the prepared photocatalyst can show extremely high catalysis activity and product selectivity in a test of photocatalysis selective phenylcarbinol oxidation for benzaldehyde preparation.
Description
Technical field
The present invention relates to nano material is prepared and photocatalysis technology field, and in particular to a kind of oxygen of load gold nano particle
Change cerium nanofiber photocatalyst and preparation method thereof.
Background technology
Photocatalysis technology can be realized that substituting thermal source using solar energy drives organic catalytic reaction for organic reaction, it
The important green sustainable chemistry of a class is represented, is expected to be applied to the light compositing of essential industry chemicals, with extremely important
Energy-conserving and environment-protective meaning.Therefore, developing high efficiency photocatalyst is used for sun optical drive organic catalytic reaction, improves luminous energy to change
It is field focus of interest to learn transformation of energy efficiency.
Ceria (CeO2) as a kind of important rare earth material, because with good oxygen migration ability, Ce3+/Ce4+Between
Mutual conversion characteristic and the features such as store oxygen property, be easily formed Lacking oxygen, be applied in numerous areas, especially make
For catalyst, it is widely used as active phase, carrier, composite catalyzing material etc., is applied to many catalytic fields, including vehicle exhaust
Purification, water-gas shift reaction, organic synthesis catalysis, photocatalysis etc..However, CeO2As the property that catalysis material is shown
Energy is simultaneously unsatisfactory, because its bandgap energy wider (～3.2eV), carrier conductivity is relatively low, so as to limit it in light
Application in terms of catalysis.In order to make full use of solar energy, scholars being all expansion CeO2The research of absorbing wavelength scope, in
It is nano Ce O2Various method of modifying also arise at the historic moment.
On the other hand, in recent years, surface plasma body resonant vibration (the surface plasmon of noble metal nano particles
Resonance, SPR) domestic and international researchers pole is caused to the effect that significantly increases of the visible light photocatalysis active of semiconductor
Big interest.2008, and Japanese AWAZU etc. [J.Am.Chem.Soc., 2008,130 (5):1676-1680.] have developed
Visible region has the Ag/TiO of wide spectrum Absorption Characteristics2Catalysis material, finds the noble metal nano particles such as Au, Ag
SPR properties have obvious improvement result to the photocatalytic activity of semiconductor.Also, nm of gold is obtained in organic catalysis field
Oxidation reaction, reduction reaction, Chirality Reaction and other reactions are all shown good catalytic performance by extensive concern, use valency
The Au catalyst of lattice relative moderate replaces Pd, Pt, Rh, and important meaning is respectively provided with scientific research and industrial production.Therefore,
Design prepares CeO2Nanomaterial loadings golden nanometer particle obtains a kind of new and effective photocatalysis for photocatalysis organic reaction
Agent, strengthens catalyst and the utilization rate of light is had very important significance.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of cerium oxide nano fiber optic of load gold nano particle is urged
Agent and preparation method thereof, preparation method is simply controllable, the obtained catalyst catalytic selectivity under simulated solar light irradiation
Very high catalysis activity and selectivity of product is shown in the test of Oxybenzene methyl alcohol producing benzaldehyde.
To realize object above, the present invention is achieved by the following technical programs：
A kind of cerium oxide nano fiber photocatalyst of load gold nano particle, golden nanometer particle uniform load is in cerium oxide
Nanofiber surface, a diameter of 200-400nm of the cerium oxide nano fiber, a diameter of 10- of the golden nanometer particle
80nm, the load capacity of the golden nanometer particle is 0.1-2.5wt%.
The preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle, step is as follows：
1) spinning solution is prepared：Weigh PVP (PVP-K90), cerous nitrate and gold chloride respectively to be added in DMF, room temperature is stirred
Mix and formed after 12-24h spinning solution, PVP mass fractions are 8-12%, Ce (NO in solution3)3Concentration is 0.5mol/L, HAuCl4
With Ce (NO3)3Mol ratio 1:600-1:60；
2) Ce (NO are prepared3)3/HAuCl4/ PVP nanofibers：Spinning solution is moved into into the syringe with No. 21 syringe needles
In, the distance between syringe needle and receiver board are 15cm, and applied voltage is 20kV, and, at 18-25 DEG C, humidity is in 10- for control room temperature
30%, prepare Ce (NO3)3/HAuCl4/ PVP nanofibers；
3) it is heat-treated：First by Ce (NO3)3/HAuCl4/ PVP nanofibers are warming up to 100 DEG C, are incubated 5h, then heat up
To 200 DEG C of insulation 1h, then 500 DEG C of insulation 2h are warming up to, room temperature is finally down to naturally, that is, obtain the oxidation of load gold nano particle
Cerium nanofiber photocatalyst.
Preferably, the step 2) in adjustment solution feeding rate be 0.5mL/h.
Preferably, the step 3) in heating rate be 1-2 DEG C/min.
The present invention compared with prior art, has the advantages that：
1st, DMF is used as solvent used in the present invention, and beneficial to the dissolving of cerous nitrate, acceleration spins the solidification of fiber, it is to avoid fine
Be bonded together between dimension；
2nd, golden nanometer particle uniform load is prepared photochemical catalyst, Jenner's grain of rice by the present invention in cerium oxide nano fiber surface
Sub- load capacity can obtain high efficiency photochemical catalyst in the range of 0.1-2.5wt% by loading minimal amount of golden nanometer particle,
Reduce catalyst cost；
3rd, the cerium oxide nano fiber photocatalyst of load gold nano particle prepared by the present invention, in ultraviolet-visible width light
Spectrum region has significant optical absorption property, enhances utilization rate of the catalyst to light, greatly improves solar energy and is converted to
The efficiency of chemical energy；
4th, the photochemical catalyst for preparing is used for into photocatalysis to selectively Oxybenzene methyl alcohol producing benzaldehyde, it shows very high urging
Change activity and selectivity of product.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the pure zirconia cerium nanofiber (CeO without load gold nano particle prepared by embodiment 12- 0Au) sweep
Retouch electron microscope (SEM) photo.
Fig. 2 is the cerium oxide nano fiber (CeO of load 0.25wt% golden nanometer particles prepared by embodiment 22-0.25Au)
SEM (SEM) photo of photochemical catalyst.
Fig. 3 is the cerium oxide nano fiber (CeO of load 0.5wt% golden nanometer particles prepared by embodiment 32- 0.5Au) light
SEM (SEM) photo of catalyst.
Fig. 4 is the cerium oxide nano fiber (CeO of load 1wt% golden nanometer particles prepared by embodiment 42- 1Au) photocatalysis
SEM (SEM) photo of agent.
Fig. 5 is the cerium oxide nano fiber (CeO of load 2.5wt% golden nanometer particles prepared by embodiment 52- 2.5Au) light
SEM (SEM) photo of catalyst.
Fig. 6 is X-ray diffraction (XRD) figure of five kinds of different nanofiber photocatalysts prepared by embodiment 1-5.
Fig. 7 is the ultraviolet-visible absorption spectroscopy of five kinds of different nanofiber photocatalysts prepared by embodiment 1-5.
Specific embodiment
To make purpose, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
The a part of embodiment of the present invention, rather than the embodiment of whole.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
Embodiment 1：
The preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle, step is as follows：
(1) 2.6054g Ce (NO are weighed respectively3)3·H2O and 1.6g PVP so as in being dissolved in 12mL DMF, Ran Hou
24h is stirred under room temperature and obtains spinning solution；
(2) spinning solution that step (1) is prepared is moved in syringe, and from No. 21 syringe needles, syringe needle internal diameter is 0.51mm,
It is 20kV to control spinning voltage, and sample introduction speed is 0.5mL/min, and the distance of syringe needle to receiver board is 15cm, controls indoor temperature
At 18 DEG C -25 DEG C, below 30%, spinning obtains Ce (NO to humidity3)3/ PVP nanofibers；
(3) Ce (NO for obtaining spinning in step (2)3)3/ PVP nanofibers, heat 5h in 100 DEG C of air, then enter
Row temperature programming twice, heating rate is 2 DEG C/min, is first warmed up to 200 DEG C, insulation 1h, is then warmed up to 500 DEG C, insulation 3h,
Room temperature is finally naturally cooled to, that is, obtains pure zirconia cerium (CeO2- 0Au) nanofiber.
Embodiment 2：
The preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle, step is as follows：
(1) 2.6054g Ce (NO are weighed respectively3)3·H2O and 1.6g PVP so as in being dissolved in 12mL DMF, Ran Houjia
Enter the chlorauric acid solution that 133 μ l concentration are 0.1mol/L, 12h is stirred at room temperature and obtains spinning solution；
(2) spinning solution that step (1) is prepared is moved in syringe, and from No. 21 syringe needles, syringe needle internal diameter is 0.51mm,
It is 20kV to control spinning voltage, and sample introduction speed is 0.5mL/min, and the distance of syringe needle to receiver board is 15cm, controls indoor temperature
At 18 DEG C -25 DEG C, below 30%, spinning obtains Ce (NO to humidity3)3/HAuCl4/ PVP nanofibers；
(3) Ce (NO for obtaining spinning in step (2)3)3/HAuCl4/ PVP nanofibers, heat in 100 DEG C of air
5h, then carry out temperature programming twice, heating rate is 1 DEG C/min, is first warmed up to 200 DEG C, insulation 1h, be then warmed up to 500 DEG C,
Insulation 3h, finally naturally cools to room temperature, that is, obtain loading the cerium oxide nano fiber (CeO of 0.25wt% golden nanometer particles2-
0.25Au) photochemical catalyst.
Embodiment 3：
The preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle, step is as follows：
(1) 2.6054g Ce (NO are weighed respectively3)3·H2O and 1.6g PVP so as in being dissolved in 12mL DMF, Ran Houjia
Enter the chlorauric acid solution that 265 μ l concentration are 0.1mol/L, 12h is stirred at room temperature and obtains spinning solution；
(2) spinning solution that step (1) is prepared is moved in syringe, and from No. 21 syringe needles, syringe needle internal diameter is 0.51mm,
It is 20kV to control spinning voltage, and sample introduction speed is 0.5mL/min, and the distance of syringe needle to receiver board is 15cm, controls indoor temperature
At 18 DEG C -25 DEG C, below 30%, spinning obtains Ce (NO to humidity3)3/HAuCl4/ PVP nanofibers；
(3) Ce (NO for obtaining spinning in step (2)3)3/HAuCl4/ PVP nanofibers, heat in 100 DEG C of air
5h, then carry out temperature programming twice, heating rate is 1 DEG C/min, is first warmed up to 200 DEG C, insulation 1h, be then warmed up to 500 DEG C,
Insulation 3h, finally naturally cools to room temperature, that is, obtain loading the cerium oxide nano fiber (CeO of 0.5wt% golden nanometer particles2-
0.5Au) photochemical catalyst.
Embodiment 4：
The preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle, step is as follows：
(1) 2.6054g Ce (NO are weighed respectively3)3·H2O and 1.6g PVP so as in being dissolved in 12mL DMF, Ran Houjia
Enter the chlorauric acid solution that 535 μ l concentration are 0.1mol/L, 12h is stirred at room temperature and obtains spinning solution；
(2) spinning solution that step (1) is prepared is moved in syringe, and from No. 21 syringe needles, syringe needle internal diameter is 0.51mm,
It is 20kV to control spinning voltage, and sample introduction speed is 0.5mL/min, and the distance of syringe needle to receiver board is 15cm, controls indoor temperature
At 18 DEG C -25 DEG C, below 30%, spinning obtains Ce (NO to humidity3)3/HAuCl4/ PVP nanofibers；
(3) Ce (NO for obtaining spinning in step (2)3)3/HAuCl4/ PVP nanofibers, heat in 100 DEG C of air
5h, then carry out temperature programming twice, heating rate is 2 DEG C/min, is first warmed up to 200 DEG C, insulation 1h, be then warmed up to 500 DEG C,
Insulation 3h, finally naturally cools to room temperature, that is, obtain loading the cerium oxide nano fiber (CeO of 1wt% golden nanometer particles2-1Au)
Photochemical catalyst.
Embodiment 5：
The preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle, step is as follows：
(1) 2.6054g Ce (NO are weighed respectively3)3·H2O and 1.6g PVP so as in being dissolved in 12mL DMF, Ran Houjia
Enter the chlorauric acid solution that 1.379ml concentration is 0.1mol/L, 24h is stirred at room temperature and obtains spinning solution；
(2) spinning solution that step (1) is prepared is moved in syringe, and from No. 21 syringe needles, syringe needle internal diameter is 0.51mm,
It is 20kV to control spinning voltage, and sample introduction speed is 0.5mL/min, and the distance of syringe needle to receiver board is 15cm, controls indoor temperature
At 18 DEG C -25 DEG C, below 30%, spinning obtains Ce (NO to humidity3)3/HAuCl4/ PVP nanofibers；
(3) Ce (NO for obtaining spinning in step (2)3)3/HAuCl4/ PVP nanofibers, heat in 100 DEG C of air
5h, then carry out temperature programming twice, heating rate is 1 DEG C/min, is first warmed up to 200 DEG C, insulation 1h, be then warmed up to 500 DEG C,
Insulation 3h, finally naturally cools to room temperature, that is, obtain loading the cerium oxide nano fiber (CeO of 2.5wt% golden nanometer particles2-
2.5Au) photochemical catalyst.
The pattern and structure of the target product prepared to embodiment of the present invention 1-5 using SEM and XRD is characterized, and SEM shines
Piece as Figure 1-5, as can be seen from the figure cerium oxide nano fibre diameter be 200-400nm, golden nanometer particle uniform load
In cerium oxide nano fiber surface, wherein the size of golden nanometer particle is in 10-80nm, as gold loading increases, Jenner's grain of rice
Sub- size increase.Fig. 6 is XRD spectrum, it was demonstrated that prepared photochemical catalyst contains cerium oxide and golden two kinds of crystallographic components, with
Golden nanometer particle load capacity increases, and the diffraction maximum of Au gradually strengthens.
Using golden nanometer particle in the target product that inductively coupled plasma (ICP) is prepared to embodiment of the present invention 2-5
Load capacity detected that testing result is shown in Table 1.
Table 1 detects the gold loading in photochemical catalyst prepared by embodiment 2-5 using ICP
From table 1 it follows that in embodiment of the present invention 2-5 prepare target product in golden nanometer particle load capacity with
Theoretical gold loading is substantially consistent.
Target product prepared by embodiment of the present invention 1-5 is tested using ultraviolet-uisible spectrophotometer, it is ultraviolet can
Absorption spectrum collection of illustrative plates is seen as shown in fig. 7, it can be seen that after load gold nano particle, catalyst is in visible region
There is obvious absworption peak to occur, and with the increase of gold content, absworption peak gradually strengthens, this will greatly improve sunshine utilization
Rate.
Target product prepared by embodiment of the present invention 1-5 is for the experiment of catalysis oxidation phenmethylol producing benzaldehyde.In illumination
Under the conditions of, with phenmethylol as raw material, acetonitrile is reaction dissolvent, and air is oxidant, is received with the cerium oxide of load gold nano particle
Rice fiber photocatalyst selective catalytic oxidation phenmethylol generates benzaldehyde, reacts 6h, investigates in the load of different golden nanometer particles
Under amount, the selectivity of the conversion rate of catalytic oxidation and reaction.Experimental result is shown in Table 2.
The impact that the different golden nanometer particle load capacity of table 2 are reacted selective catalytic oxidation phenmethylol
From Table 2, it can be seen that catalytic reaction generation product is single, the cerium oxide nano with unsupported golden nanometer particle
Fiber photocatalyst is compared, and the photochemical catalyst catalytic efficiency for having loaded golden nanometer particle is significantly increased.When golden nanometer particle is born
When carrying capacity is 0.5wt%, its reaction conversion rate is about 4 times of blank cerium oxide nano fiber photocatalyst, and catalytic condition
Gently, have great significance in the industrial production that aldehyde compound is prepared in alcohol compound selective oxidation.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply these entities or deposit between operating
In any this actual relation or order.And, term " including ", "comprising" or its any other variant are intended to
Nonexcludability is included, so that a series of process, method, article or equipment including key elements not only will including those
Element, but also including other key elements being not expressly set out, or also include for this process, method, article or equipment
Intrinsic key element.In the absence of more restrictions, the key element for being limited by sentence "including a ...", it is not excluded that
Also there is other identical element in process, method, article or equipment including the key element.
Above example only to illustrate technical scheme, rather than a limitation；Although with reference to the foregoing embodiments
The present invention has been described in detail, it will be understood by those within the art that：It still can be to aforementioned each enforcement
Technical scheme described in example is modified, or carries out equivalent to which part technical characteristic；And these modification or
Replace, do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution.
Claims (4)
1. a kind of cerium oxide nano fiber photocatalyst of load gold nano particle, it is characterised in that golden nanometer particle is uniformly born
Be loaded in cerium oxide nano fiber surface, a diameter of 200-400nm of the cerium oxide nano fiber, the golden nanometer particle it is straight
Footpath is 10-80nm, and the load capacity of the golden nanometer particle is 0.1-2.5wt%.
2. the preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle as claimed in claim 1, it is special
Levy and be, step is as follows：
1) spinning solution is prepared：PVP (PVP-K90), cerous nitrate and gold chloride are weighed respectively to be added in DMF, and 12- is stirred at room temperature
Spinning solution is formed after 24h, PVP mass fractions are 8-12%, Ce (NO in solution3)3Concentration is 0.5mol/L, HAuCl4And Ce
(NO3)3Mol ratio be 1:600-1:60；
2) Ce (NO are prepared3)3/HAuCl4/ PVP nanofibers：Spinning solution is moved in the syringe with No. 21 syringe needles, pin
The distance between head and receiver board are 15cm, and applied voltage is 20kV, and, at 18-25 DEG C, humidity is in 10-30%, system for control room temperature
It is standby go out Ce (NO3)3/HAuCl4/ PVP nanofibers；
3) it is heat-treated：First by Ce (NO3)3/HAuCl4/ PVP nanofibers are warming up to 100 DEG C, are incubated 5h, then heat to 200
DEG C insulation 1h, then 500 DEG C of insulation 2h are warming up to, room temperature is finally down to naturally, i.e. the cerium oxide of acquisition load gold nano particle is received
Rice fiber photocatalyst.
3. the preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle as claimed in claim 2, it is special
Levy and be, the step 2) in adjustment solution feeding rate be 0.5mL/h.
4. the preparation method of the cerium oxide nano fiber photocatalyst of load gold nano particle as claimed in claim 2, it is special
Levy and be, the step 3) in heating rate be 1-2 DEG C/min.
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