CN110102312A - A kind of one-dimensional cuprous oxide/silver/zinc oxide nanometer rods optic catalytic composite material and the preparation method and application thereof - Google Patents
A kind of one-dimensional cuprous oxide/silver/zinc oxide nanometer rods optic catalytic composite material and the preparation method and application thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 98
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 17
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title description 7
- 239000002131 composite material Substances 0.000 title description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 230000001699 photocatalysis Effects 0.000 claims abstract description 24
- 238000007146 photocatalysis Methods 0.000 claims abstract description 23
- 239000002073 nanorod Substances 0.000 claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006722 reduction reaction Methods 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 229910000336 copper(I) sulfate Inorganic materials 0.000 claims description 14
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 9
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008569 process 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/23—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention belongs to photochemical catalyst preparation technical field, it is related to a kind of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst and preparation method thereof and its photocatalysis CO2One-dimensional Cu is prepared by the method for simple hydro-thermal method and electronation in the application that reduction generates CO2O/Ag/ZnO nano-rod photo-catalyst.Prepared one-dimensional Cu2O/ZnO and Cu2O/Ag/ZnO nano-rod photo-catalyst all has photocatalysis CO more higher than One-Dimensional ZnO nano-rod photo-catalyst2Reducing property, product are CO.In addition, prepared one-dimensional Cu2O/Ag/ZnO nano-rod photo-catalyst has higher photocatalysis CO under ultraviolet-visible irradiation2Reducing property and stability.The method of the present invention preparation process is simple, and reaction condition is mild, to photocatalysis CO2Reduction has important practical application value, is conducive to the sustainable development of environment and the energy.
Description
Technical field
The invention belongs to photochemical catalyst preparation technical fields, and in particular to a kind of one-dimensional cuprous oxide/silver/zinc oxide nanometer
The preparation method and applications of rod photo-catalyst are in photocatalysis CO2Reduction generates CO.
Background technique
Energy crisis and problem of environmental pollution it is increasingly prominent, promote the rapid development of catalytic field.Development and utilization are clear
The clean renewable sunlight energy realizes that efficient catalysis reaction is imperative.Wherein, photocatalysis CO2The development of reduction is expected to
It plays an important role to solve this two large problems.One-dimensional nano structure material, especially nanometer rods have big specific surface area,
The direct channel of electric current transmission can be provided, be conducive to the separation of photo-generate electron-hole, further increase electron transport rate,
It is the catalysis material of a kind of great potential using value.Zinc oxide (ZnO) is a kind of semiconductor material with direct band gap,
And preparation cost is low, environmental-friendly, but since its forbidden bandwidth is wider (about 3.37 eV or so), can only respond in ultra-violet (UV) band.
And cuprous oxide (Cu2O) possess relatively narrow forbidden bandwidth (2.2 eV), making it under visible light has relatively good photocatalysis special
Property.In addition, carried metal co-catalyst can form semiconductor-metal heterojunction structure on photochemical catalyst, it is lower using metal
Fermi level, realize efficiently separating for light induced electron and hole, the efficiency of photocatalytic system can be advanced optimized.Therefore, originally
A kind of easy preparation method is developed in invention, and cuprous oxide and metallic silver are loaded on Synthetic Routes of One-dimensional ZnO Nanorods, study its
Photocatalysis CO under ultraviolet-visible2Reduction activation.The result shows that after having loaded cuprous oxide and metallic silver, one-dimensional Cu2O/Ag/
ZnO nanorod photochemical catalyst has embodied the photocatalysis CO significantly improved2Reduction activation, and it is with good stability, five
Secondary circulation rear catalyst activity does not change much.
Summary of the invention
The purpose of the present invention is to provide a kind of simple production process, the one-dimensional Cu of environmental-friendly, regular pattern2O/
Ag/ZnO nanometer rods optic catalytic composite material and preparation method thereof and the composite material are in photocatalysis CO2The application of reduction.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst, the catalyst have very under ultraviolet-visible irradiation
Good photocatalysis CO2Reduction.
The preparation method of the one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst, comprising the following steps:
(1) hydro-thermal method prepares One-Dimensional ZnO nanometer rods
By quantitative Zn (NO3)2·6H2O, water and ethyl alcohol are mixed, and the ammonium hydroxide tune pH value of 28wt% is added.Stirring 180 minutes
Afterwards, acquired solution is added in the stainless steel autoclave for the Teflon lining that capacity is 100 mL.By autoclave at 160 DEG C
It is lower to be kept for 10 hours, cooled to room temperature.White depositions are collected, is respectively washed three times, is dried with second alcohol and water, ground, calcining,
Obtain One-Dimensional ZnO photochemical catalyst；
(2) chemical reduction method prepares one-dimensional Cu2O/Ag/ZnO nanometer rods:
Take step (1) obtain in One-Dimensional ZnO photochemical catalyst ultrasonic disperse into 80 mL deionized waters, be added dropwise respectively
Cu2SO4·5H2O solution and NaOH solution are stirred by ultrasonic 20 minutes.Then AgNO is added dropwise3Solution is stirred by ultrasonic 20 minutes.Again
Ascorbic acid is added, stirs 20 minutes, centrifugation is washed with deionized, vacuum drying, obtains one-dimensional Cu2O/Ag/ZnO nanometers
Stick.
In the step (1), in step (1), Zn (NO3)2·6H2The quality of O is 5.95 g, and the mixing of second alcohol and water is molten
The volume ratio of second alcohol and water is 4:5 in liquid.
In the step (1), pH value 8.
In the step (1), drying temperature is 60 DEG C.
In the step (1), calcination condition is 350 DEG C of 3 h of calcining under the air atmosphere in tube furnace.
In the step (2), the ascorbic acid quality of addition is 30 mg, the Cu of addition2SO4·5H2O solution and NaOH are molten
The concentration of liquid is respectively 0.05 and 0.1 mol/L, Cu2SO4·5H2The volume ratio of O solution and NaOH solution is 1:1.
In the step (2), Cu2SO4·5H2O and AgNO3Amount ratio be, with the molar ratio computing of Cu ion and Ag ion
Are as follows: Cu/Ag=1:4 or 2:3 or 4:1.
One-dimensional Cu prepared by the present invention2O/Ag/ZnO photochemical catalyst is used to irradiate lower photocatalysis CO under ultraviolet-visible2Reduction
Reaction, the specific steps are as follows: take the one-dimensional Cu of 10 mg2O/Ag/ZnO photochemical catalyst is placed in reactor, while being put in the reactor
Set a 2 mL centrifuge tubes.In CO2In atmosphere, 0.5 mL water is injected in the centrifuge tube into reactor.Reactor is placed in purple
Illumination 4 hours under outer visible light take 1 mL gas inlet analysis of hplc, carry out qualitative, quantitative by retention time and peak area
Analysis.
The present invention prepares one-dimensional Cu using above method2O/Ag/ZnO photochemical catalyst, the photochemical catalyst is in ultraviolet-visible
Under irradiation, the light induced electron and Cu on ZnO can be made2The photohole of O is combined with the charge transmission mode of Z-scheme, is promoted
Photo-generated carrier separation.Simultaneously using the metallic silver of chemical reduction method load, ZnO and Cu can either be further captured2The conduction band of O
The light induced electron of upper generation, and can be used as the progress of the active site catalysis reaction of reaction.The introducing of this multi-component material,
On the one hand promote photo-generate electron-hole to efficiently separating, fully played the catalytic performance of semiconductor, on the other hand can mention
For more CO2The progress for activating site catalysis reaction, finally makes one-dimensional Cu2O/Ag/ZnO nanometer rods optic catalytic composite material tool
There is better CO2Reducing property and stability.In addition, the present invention also has the advantages that
(1) of the invention by one-dimensional Cu2O/Ag/ZnO photochemical catalyst is used for photocatalysis CO2Reduction system, catalysis effect with higher
Rate, prepared Cu2O/Ag/ZnO photochemical catalyst has photocatalysis CO more higher than One-Dimensional ZnO photochemical catalyst2Reducing property has
Conducive to the sustainable development of environment and the energy.
(2) one-dimensional Cu2The photocatalysis to selectively height of O/Ag/ZnO photochemical catalyst, good cycle, low manufacture cost, production
Simple process macroscopical can be prepared.
Detailed description of the invention
Fig. 1 is the SEM figure of different materials respectively: the SEM figure of (A) One-Dimensional ZnO photochemical catalyst；(B) one-dimensional Cu2O/ZnO light
The SEM of catalyst schemes；(C) one-dimensional Cu2The SEM of O/Ag/ZnO photochemical catalyst schemes;
Fig. 2 is the X ray diffracting spectrum of different materials；It (A) include One-Dimensional ZnO photochemical catalyst, and load different proportion Cu2O
One-dimensional Cu2O/ZnO photochemical catalyst；It (B) include one-dimensional 1wt% Cu2O/ZnO photochemical catalyst and the different Cu of load2O, Ag ratio
One-dimensional Cu2O/Ag/ZnO photochemical catalyst；
Fig. 3 is the UV-vis DRS spectrum of different materials；(A) One-Dimensional ZnO photochemical catalyst, and load different proportion Cu2O
One-dimensional Cu2O/ZnO photochemical catalyst；It (B) include one-dimensional 1wt% Cu2O/ZnO photochemical catalyst and the different Cu of load2O, Ag ratio
One-dimensional Cu2O/Ag/ZnO photochemical catalyst；
CO of Fig. 4 different materials under ultraviolet-visible irradiation2Reduction activation；
The one-dimensional Cu of Fig. 52Multiple circulation activity figure of the O/Ag/ZnO photochemical catalyst under ultraviolet-visible irradiation.
Specific embodiment
A kind of preparation method of one-dimensional cuprous oxide/silver/zinc oxide nanometer rods optic catalytic composite material,
Include the following steps
(1) hydro-thermal method prepares One-Dimensional ZnO nanometer rods:
By 5.95 g Zn (NO3)2·6H2O and the mixing of 100 mL water and 80 mL ethanol solutions, add the ammonium hydroxide tune pH value of 28wt%
To 8.After stirring 180 minutes, it is added in the stainless steel autoclave for the Teflon lining that capacity is 100 mL.Autoclave is existed
It is kept for 10 hours at 160 DEG C, cooled to room temperature.White depositions are collected, are respectively washed three times with second alcohol and water, 60 DEG C of bakings
Dry, grinding, 350 DEG C of 3 h of calcining under air atmosphere, obtain One-Dimensional ZnO photochemical catalyst in tube furnace；
(2) chemical reduction method prepares one-dimensional Cu2O/ZnO nanometer rods:
The One-Dimensional ZnO photochemical catalyst ultrasonic disperse for taking 80 mg steps (1) to obtain is added dropwise respectively into 80 mL deionized waters
Cu2SO4·5H2O solution (0.05 mol/L) and NaOH solution (0.1 mol/L) are stirred by ultrasonic 20 minutes.It is anti-bad that 30 mg are added
Hematic acid stirs 20 minutes, and centrifugation is washed with deionized, vacuum drying at 22-25 DEG C obtains one-dimensional Cu2O/ZnO nanometers
Stick；
(3) chemical reduction method prepares one-dimensional Cu2O/Ag/ZnO nanometer rods:
The One-Dimensional ZnO photochemical catalyst ultrasonic disperse for taking 80 mg steps (1) to obtain is added dropwise respectively into 80 mL deionized waters
Cu2SO4·5H2O solution (0.05 mol/L) and NaOH solution (0.1 mol/L) are stirred by ultrasonic 20 minutes.Then AgNO is added dropwise3
Solution (0.1 mol/L) is stirred by ultrasonic 20 minutes.30 mg ascorbic acid are added, are stirred 20 minutes, deionized water is used in centrifugation
It washs, vacuum drying at 22-25 DEG C obtains one-dimensional Cu2O/Ag/ZnO nanometer rods.
One-dimensional Cu prepared by the present invention2O/Ag/ZnO photochemical catalyst is used to irradiate lower photocatalysis CO under ultraviolet-visible2Reduction
Reaction, the specific steps are as follows: take the one-dimensional Cu of 10 mg2O/Ag/ZnO photochemical catalyst is placed in reactor, while being put in the reactor
Set a 2 mL centrifuge tubes.In CO2In atmosphere, 0.5 mL water is injected in the centrifuge tube into reactor.Reactor is placed in purple
Illumination 4 hours under outer visible light take 1 mL gas inlet analysis of hplc, carry out qualitative, quantitative by retention time and peak area
Analysis.
The present invention is further illustrated using specific embodiment below, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
Prepare One-Dimensional ZnO nanometer rods:
By 5.95 g Zn (NO3)2·6H2O and the mixing of 100 mL water and 80 mL ethanol solutions, adding concentration is 28% ammonium hydroxide tune
PH value is saved to 8.After stirring 180 minutes, three parts of solution point are added to the stainless steel height for the Teflon lining that capacity is 100 mL
It presses in kettle.Autoclave is kept for 10 hours at 160 DEG C, cooled to room temperature.White depositions are collected, with second alcohol and water
It respectively washes three times, 60 DEG C of drying, grinding, 350 DEG C of 3 h of calcining under air atmosphere, obtain One-Dimensional ZnO photocatalysis in tube furnace
Agent；
Photocatalysis CO2Reduction experiment:
It takes 10 mg One-Dimensional ZnO photochemical catalysts to be placed in reactor, while placing a 2 mL centrifuge tubes in the reactor.In CO2
In atmosphere, 0.5 mL water is injected in the centrifuge tube into reactor.Reactor is placed in illumination 4 hours under ultraviolet-visible, is produced
Raw CO content is 1.338 μm of ol/g.
Embodiment 2
Prepare one-dimensional Cu2O/ZnO nanometer rods (1Cu/Zn):
It takes 80 mg One-Dimensional ZnO nano-rod photo-catalyst ultrasonic disperses into 80 mL deionized waters, 200 μ L is added dropwise respectively
Cu2SO4·5H2O solution (0.05 mol/L) and NaOH solution (0.1 mol/L) are stirred by ultrasonic 20 minutes.It is anti-bad that 30 mg are added
Hematic acid stirs 20 minutes, and centrifugation is washed with deionized, vacuum drying at 22-25 DEG C obtains one-dimensional Cu2O/ZnO nanometer rods
Photochemical catalyst；
Photocatalysis CO2Reduction experiment:
Take the one-dimensional Cu of 10 mg2O/ZnO photochemical catalyst is placed in reactor, while placing a 2 mL centrifuge tubes in the reactor.
In CO2In atmosphere, 0.5 mL water is injected in the centrifuge tube into reactor.It is small that reactor is placed in illumination 4 under ultraviolet-visible
When, generation CO content is 8.143 μm of ol/g.
Embodiment 3
Prepare one-dimensional Cu2O/Ag/ZnO nanometer rods (0.4Cu/0.6Ag/Zn):
Take the one-dimensional Cu of 80 mg280 μ L are added dropwise into 80 mL deionized waters in O/Ag/ZnO photochemical catalyst ultrasonic disperse respectively
Cu2SO4·5H2O solution (0.05 mol/L) and NaOH solution (0.1 mol/L) are stirred by ultrasonic 20 minutes.Then 60 μ L are added dropwise
AgNO3Solution (0.1 mol/L) is stirred by ultrasonic 20 minutes.30 mg ascorbic acid are added, are stirred 20 minutes, centrifugation is spent
Ion water washing, vacuum drying at 22-25 DEG C, obtains one-dimensional Cu2O/Ag/ZnO nanometer rods (Cu2SO4·5H2O and AgNO3Use
Ratio is measured, with the molar ratio computing of Cu ion and Ag ion are as follows: Cu/Ag=2:3).
Photocatalysis CO2Reduction experiment:
Take the one-dimensional Cu of 10 mg2O/Ag/ZnO photochemical catalyst is placed in reactor, while placing a 2 mL centrifugation in the reactor
Pipe.In CO2In atmosphere, 0.5 mL water is injected in the centrifuge tube into reactor.Reactor is placed in illumination 4 under ultraviolet-visible
Hour, generation CO content is 13.453 μm of ol/g.
Embodiment 4
Prepare one-dimensional Cu2O/Ag/ZnO nanometer rods (0.8Cu/0.2Ag/Zn):
Take the one-dimensional Cu of 80 mg2160 μ L are added dropwise into 80mL deionized water in O/Ag/ZnO photochemical catalyst ultrasonic disperse respectively
Cu2SO4·5H2O solution (0.05 mol/L) and NaOH solution (0.1 mol/L) are stirred by ultrasonic 20 minutes.Then 20 μ L are added dropwise
AgNO3Solution (0.1 mol/L) is stirred by ultrasonic 20 minutes.30 mg ascorbic acid are added, are stirred 20 minutes, centrifugation is spent
Ion water washing, vacuum drying at 22-25 DEG C, obtains one-dimensional Cu2O/Ag/ZnO nanometer rods (Cu2SO4·5H2O and AgNO3Use
Ratio is measured, with the molar ratio computing of Cu ion and Ag ion are as follows: Cu/Ag=4:1)
Photocatalysis CO2Reduction experiment:
Take the one-dimensional Cu of 10 mg2O/Ag/ZnO photochemical catalyst is placed in reactor, while placing a 2 mL centrifugation in the reactor
Pipe.In CO2In atmosphere, 0.5 mL water is injected in the centrifuge tube into reactor.Reactor is placed in illumination 4 under ultraviolet-visible
Hour, generation CO content is 4.483 μm of ol/g.
Embodiment 5
Prepare one-dimensional Cu2O/Ag/ZnO nanometer rods (0.2Cu/0.8Ag/Zn):
Take the one-dimensional Cu of 80 mg240 μ L are added dropwise into 80 mL deionized waters in O/Ag/ZnO photochemical catalyst ultrasonic disperse respectively
Cu2SO4·5H2O solution (0.05 mol/L) and NaOH solution (0.1 mol/L) are stirred by ultrasonic 20 minutes.Then 80 μ L are added dropwise
AgNO3Solution (0.1 mol/L) is stirred by ultrasonic 20 minutes.30 mg ascorbic acid are added, are stirred 20 minutes, centrifugation is spent
Ion water washing, vacuum drying at 22-25 DEG C, obtains one-dimensional Cu2O/Ag/ZnO nanometer rods (Cu2SO4·5H2O and AgNO3Use
Ratio is measured, with the molar ratio computing of Cu ion and Ag ion are as follows: Cu/Ag=1:4)
Photocatalysis CO2Reduction experiment:
Take the one-dimensional Cu of 10 mg2O/Ag/ZnO photochemical catalyst is placed in reactor, while placing a 2 mL centrifugation in the reactor
Pipe.In CO2In atmosphere, 0.5 mL water is injected in the centrifuge tube into reactor.Reactor is placed in illumination 4 under ultraviolet-visible
Hour, generation CO content is 9.049 μm of ol/g.
The related experiment result of each material prepared by the present invention is as shown in one of Fig. 1-5.
Schemed from the SEM of Fig. 1 as can be seen that using chemical reduction method loaded Cu2O and Ag does not destroy the style of ZnO, and
And after loading, the surface ZnO shows slightly coarse, this demonstrate that Cu2O and Ag can be loaded to successfully on ZnO nanorod, be also demonstrated
Materials synthesis success.
A figure in Fig. 2, each material X ray diffracting spectrum illustrate that the ZnO nanorod of synthesis has one very strong (101)
Peak.B in Fig. 2 schemes, after loaded Ag it can be seen that (111) peak of Ag, this also further demonstrates that materials synthesis success.
The one-dimensional Cu of the cuprous oxide of A figure in Fig. 3, One-Dimensional ZnO and load different proportion2The UV, visible light of O/ZnO
The spectrogram that diffuses illustrates the Cu of load2O is capable of increasing ZnO in the light absorption of visible-range；B figure in Fig. 3, one-dimensional 1wt%
Cu2The one-dimensional Cu of the metallic silver and cuprous oxide of O/ZnO and load different proportion2The UV-vis DRS light of O/Ag/ZnO
Spectrogram illustrates that the metallic silver of load and cuprous oxide can adjust ZnO in the light absorption of visible-range.
The CO of Fig. 4 different materials2Reduction activation figure illustrates loaded Cu2ZnO can effectively be enhanced in UV, visible light after O and Ag
CO under light irradiation2Reducing property, product CO.
Fig. 5, one-dimensional Cu2Multiple circulation activity figure of the O/Ag/ZnO photochemical catalyst under ultraviolet-visible irradiation, illustrates one
Victoria C u2O/Ag/ZnO photochemical catalyst is with good stability.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (9)
1. a kind of preparation method of one-dimensional cuprous oxide/silver/zinc oxide photochemical catalyst, it is characterised in that: itself the following steps are included:
(1) hydro-thermal method prepares One-Dimensional ZnO nanometer rods:
By Zn (NO3)2·6H2O, in water and alcohol mixed solution, the ammonium hydroxide tune pH value of 28wt% is added；After stirring 180 minutes,
Acquired solution is added in the stainless steel autoclave for the Teflon lining that capacity is 100 mL；Autoclave is protected at 160 DEG C
10 hours are held, cooled to room temperature；White depositions are collected, is respectively washed three times, is dried with second alcohol and water, ground, calcining obtains
One-Dimensional ZnO photochemical catalyst；
(2) chemical reduction method prepares one-dimensional Cu2O/Ag/ZnO nanometer rods:
By One-Dimensional ZnO nanometer rods ultrasonic disperse obtained in step (1) into deionized water, Cu is added dropwise2SO4·5H2O solution and
NaOH solution is stirred by ultrasonic 20 minutes；AgNO is added dropwise again3Solution is stirred by ultrasonic 20 minutes；It is eventually adding ascorbic acid, is stirred
20 minutes, centrifugation was washed with deionized, vacuum drying, obtains one-dimensional Cu2O/Ag/ZnO nanometer rods.
2. the preparation method of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst according to claim 1, special
Sign is: in step (1), Zn (NO3)2·6H2The quality of O is 5.95 g, the body of second alcohol and water in the mixed solution of second alcohol and water
Product ratio is 4:5.
3. the preparation method of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst according to claim 1, special
Sign is: in step (1), pH is transferred to 8.
4. the preparation method of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst according to claim 1, special
Sign is: in step (1), the drying temperature is 60 DEG C.
5. the preparation method of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst according to claim 1, special
Sign is: in step (1), the calcination condition is 350 DEG C of 3 h of calcining under the air atmosphere in tube furnace.
6. the preparation method of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst according to claim 1, special
Sign is: the ascorbic acid quality being added in step (2) is 30 mg, the Cu of addition2SO4·5H2O solution and NaOH solution it is dense
Degree is respectively 0.05 and 0.1 mol/L, Cu2SO4·5H2The volume ratio of O solution and NaOH solution is 1:1.
7. the preparation method of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst according to claim 1, special
Sign is: in step (2), AgNO3The concentration of solution is 0.1 mol/L；Cu2SO4·5H2O and AgNO3Amount ratio be, with Cu
The molar ratio computing of ion and Ag ion are as follows: Cu/Ag=1:4 or 2:3 or 4:1.
8. the one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst obtained such as any preparation method of claim 1-7.
9. the application of one-dimensional cuprous oxide/silver/zinc oxide nano-rod photo-catalyst as claimed in claim 8, it is characterised in that:
The photochemical catalyst irradiates lower photocatalysis CO for ultraviolet-visible2Reduction.
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