CN109289875A - The ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield, preparation method and application - Google Patents
The ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield, preparation method and application Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002073 nanorod Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 238000004544 sputter deposition Methods 0.000 claims description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 229910052594 sapphire Inorganic materials 0.000 claims description 15
- 239000010980 sapphire Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000003708 ampul Substances 0.000 claims description 10
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- 239000011812 mixed powder Substances 0.000 claims description 9
- 238000005477 sputtering target Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
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- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000013077 target material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C01B3/042—Decomposition of water
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Abstract
The invention discloses a kind of ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield, including insulating substrate, ZnO nano-rod array are distributed with over the substrate, the ZnO nano-rod array is made of several ZnO nanorods；Several ZnO nanorod outer layers are WS2Film forms ZnO-WS2Compound system；The ZnO-WS2The load of compound system outer layer has CdS nano particle, forms ZnO-WS2CdS core shell nanometer stick array.The application of hydrogen is produced the present invention also provides the preparation method of the photochemical catalyst and under visible light catalytic.Photochemical catalyst of the invention has effective electronics transfer energy level, realizes quick carrier separation to improve production hydrogen activity.
Description
Technical field
The present invention relates to a kind of catalysis material, in particular to the ZnO core-shell nanometer rod array light of a kind of highly effective hydrogen yield is urged
Agent, preparation method and application.
Background technique
Photocatalysis technology has always been considered as being the effective technology for solving environment and energy problem, wherein Photocatalyzed Hydrogen Production technology
Clean hydrogen is directly split water into using solar energy, therefore researcher is dedicated to developing efficient conductor photocatalysis
Agent, wherein research structure-performance is critically important research direction.ZnO one-dimentional structure has high-specific surface area, quick carrier
Transmission path and excellent absorbing properties, receive significant attention, but at the same time, and ZnO broad-band gap, which can only absorb, accounts for the sun
The quick compound influence catalytic efficiency of ultraviolet light and semiconductor photo-generate electron-hole of light 5%.The forbidden bandwidth of CdS is 2.4eV,
It showing good visible light and produces hydrogen activity, ZnO and CdS are compound, and ZnO spectral absorption can not only be widened by forming hetero-junctions, and
And CdS photo-generate electron-hole can be made to efficiently separate, improve photocatalytic activity.WS2As typical transient metal sulfide,
With good co-catalysis performance.
Summary of the invention
Goal of the invention: narrow in order to solve existing ZnO light abstraction width, sun light utilization efficiency is low and semiconductor photoproduction is electric
The quick compound problem in sub- hole, the present invention provides a kind of highly effective hydrogen yield ZnO core-shell nanometer rod array photo catalysis agent.This hair
There is provided highly effective hydrogen yield ZnO core-shell nanometer rod array photo catalysis agent preparation methods for bright another object.The present invention also provides
The ZnO core-shell nanometer rod array photo catalysis agent of the highly effective hydrogen yield produces the application of hydrogen under visible light.
Technical solution: a kind of ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield of the present invention, including insulation
Substrate, is distributed with ZnO nano-rod array over the substrate, and the ZnO nano-rod array is made of several ZnO nanorods；If
Doing the ZnO nanorod outer layer is WS2Film forms ZnO-WS2Compound system；The ZnO-WS2The load of compound system outer layer has
CdS nano particle forms ZnO-WS2CdS core shell nanometer stick array.
Existing substrate material can be selected in insulating substrate of the present invention, needs to meet resistance to 1000-1200 DEG C of high temperature i.e.
It can.
The ZnO nano-rod array that the present invention is grown on substrate, array direction is to be in vertical distribution substantially with substrate, excellent
The average diameter for being selected as the ZnO nanorod is 300-1000nm.
The WS of the invention2Film is distributed in ZnO nanorod outer layer, it is preferable that WS2Film Average Thickness is 1-10nm.
ZnO-WS of the invention2The load of compound system outer layer has CdS nano particle, it is preferable that CdS nano particle is averaged grain
Diameter is 5-15nm.
It is Sapphire Substrate that a kind of preferred embodiment of the invention, which is the substrate,.
ZnO nano-rod array described in another preferred embodiment of the invention is that sapphire lining is grown in by vapour deposition process
On bottom.
The above-mentioned specific growing method of ZnO nano-rod array are as follows: mix ZnO powder and carbon dust according to mass ratio 1:1-3
Mixed-powder is obtained, and is put into quartzy bottom of the tube；It regard Sapphire Substrate stripping and slicing, cleaning as growth substrate；By mixed-powder and
Sapphire Substrate is put into quartz ampoule open at one end, and quartz ampoule level is pushed into tube furnace, vacuumizes and then passes to 130-
180sccm argon gas and 13-18sccm oxygen carry out pyroreaction, and temperature is 1000-1200 DEG C, reaction time 10-60min,
Reaction terminates to generate ZnO nano-rod array.
Preferably, above-mentioned WS2Film is that ZnO nanorod outer layer is carried on by sputtering mode, and what the sputtering used sets
Standby is magnetic control sputtering device, sputtering target material WS2Target, specification are 60 × 3mm, and cavity air pressure is 1-4Pa, argon flow 30-
50sccm, nitrogen flow 5-10sccm, sputtering power 80-150W, sputtering time 5-30min.
Preferably, above-mentioned CdS nano particle is carried on ZnO-WS by sputtering mode2Compound system outer layer, the sputtering
The equipment used is magnetic control sputtering device, and sputtering target material is CdS target, and specification is 60 × 3mm, and cavity air pressure is 1-4Pa, argon gas stream
Amount is 30-50sccm, nitrogen flow 5-10sccm, sputtering power 80-150W, sputtering time 5-30min.
The preparation method of the ZnO core-shell nanometer rod array photo catalysis agent of above-mentioned highly effective hydrogen yield, comprising the following steps:
(1) vapour deposition process growing ZnO nanorod arrays are used on an insulating substrate；(2) ZnO obtained in step (1)
Nanometer stick array sputters one layer of WS2Film forms ZnO-WS2Compound system；(3) in the compound system that step (2) obtains
ZnO-WS2Upper sputtering CdS nano particle forms ZnO-WS2- CdS compound system.
Preferably, in step (1), the growing method of the ZnO nano-rod array is as follows: ZnO powder and carbon dust are pressed
It is mixed to get mixed-powder according to mass ratio 1:1-3, and is put into quartzy bottom of the tube；By Sapphire Substrate stripping and slicing, cleaning as growth
Substrate；Mixed-powder and Sapphire Substrate are put into quartz ampoule open at one end, quartz ampoule level is pushed into tube furnace, taken out
Vacuum then passes to 130-180sccm argon gas and 13-18sccm oxygen carries out pyroreaction, and temperature is 1000-1200 DEG C, reaction
Time is 10-60min, and reaction terminates to generate ZnO nano-rod array.
Preferably, in step (2), the WS2Film specific is the preparation method is as follows: the equipment used is magnetron sputtering
Instrument, sputtering target material WS2Target, specification are 60 × 3mm, and cavity air pressure is 1-4Pa, argon flow 30-50sccm, nitrogen stream
Amount is 5-10sccm, sputtering power 80-150W, sputtering time 5-30min.
Preferably, in step (3), the CdS nano particle is carried on ZnO-WS by sputtering mode2Outside compound system
Layer, sputtering the equipment used is magnetic control sputtering device, and sputtering target material is CdS target, and specification is 60 × 3mm, and cavity air pressure is 1-
4Pa, argon flow 30-50sccm, nitrogen flow 5-10sccm, sputtering power 80-150W, sputtering time 5-
30min。
The ZnO core-shell nanometer rod array photo catalysis agent of above-mentioned highly effective hydrogen yield is used to produce hydrogen under visible light.
The utility model has the advantages that the present invention passes through synthesis ZnO-WS2CdS core shell nanometer rods can be absorbed ZnO by modifying CdS
Widen visible light, WS2It effectively improves visible light and produces hydrogen activity, while the evenly dispersed WS of ZnO2And CdS, constitute effective electronics
Energy level is shifted, so that obtaining efficient visible light produces hydrogen catalyst.
Detailed description of the invention
Fig. 1 is the ZnO-WS that the embodiment of the present invention 1 synthesizes2The signal of CdS core shell nanometer stick array scanning electron microscope
Figure；
Fig. 2 is the ZnO-WS that the embodiment of the present invention 1 synthesizes2The transmission electron microscope schematic diagram of CdS core shell nanometer rods；
Fig. 3 is the ZnO-WS that the embodiment of the present invention 1 synthesizes2The visible light of CdS core shell nanometer stick array produces hydrogen schematic diagram.
Specific embodiment
Technical solution of the present invention is further illustrated below with reference to embodiment.
Embodiment 1: step 1: the end ZnO for being 99.99% for purity and carbon dust be according to mass ratio 1:1 mixed grinding,
It inserts in ceramic boat；Sapphire Substrate is cut into 1.5cm × 1cm, it is clear successively to carry out acetone, dehydrated alcohol, deionized water ultrasound
It washes, and with being dried with nitrogen, as growth substrate, is then placed in length 30cm open at one end, the quartzy duct occlusion of diameter 3cm
End places cleaned Sapphire Substrate away from the quartz ampoule at the position nozzle 5cm.Quartz ampoule is integrally pushed into setting temperature
To close tube furnace, vacuumizing, and be passed through argon flow 150sccm and oxygen flow in 1050 DEG C of horizontal pipe furnaces
15sccm, after 30min reacts, ZnO nano rice stick array growth is in sapphire surface；
Step 2: using magnetic control sputtering device, ZnO nano-rod array sputters one layer of WS wherein2Film, with WS2Target is to splash
Source is penetrated, specification is 60 × 3mm, and cavity air pressure is 2Pa, argon flow 50sccm, nitrogen flow 10sccm, and sputtering power is
100W, sputtering time 8min, obtains ZnO-WS2Compound；
Step 3: utilizing magnetic control sputtering device ZnO-WS wherein2Compound sputters one layer of CdS film, is to splash with CdS target
Source is penetrated, specification is 60 × 3mm, and cavity air pressure is 2Pa, argon flow 50sccm, nitrogen flow 10sccm, and sputtering power is
100W, sputtering time 8min, obtains ZnO-WS2CdS core shell nanometer stick array, is shown in Fig. 1 and 2；
Step 4: by the acquisition product of third step weigh it is a certain amount of be transferred in photo catalysis reactor, in simulated solar irradiation
Under (optical filter for adding 420nm) carry out light-catalyzed reaction, photoactivation hydrogen production by water decomposition as evaluate photochemical catalyst activity, see
Fig. 3.
Embodiment 2: method is with embodiment 1, the difference is that the pyroreaction time of the first step is 10min, second step splashes
Penetrating the time is 10min, and the sputtering time of third step is 10min, obtained ZnO-WS2CdS core shell nanometer stick array pattern and reality
It is similar to apply example 1.
Embodiment 3: method is with embodiment 1, the difference is that the pyroreaction time of the first step is 15min, second step splashes
Penetrating the time is 8min, and cavity volume 1.5Pa, the sputtering time of third step is 15min, and cavity air pressure is 1.5Pa, is obtained
ZnO-WS2CdS core shell nanometer stick array pattern is similar to Example 1.
Embodiment 4: method is with embodiment 1, the difference is that the pyroreaction time of the first step is 45min, second step splashes
Penetrating the time is 20min, and the sputtering time of third step is 15min, obtained ZnO-WS2CdS core shell nanometer stick array pattern and reality
It is similar to apply example 1.
Embodiment 5: method is with embodiment 1, the difference is that ZnO powder and carbon dust are mixed according to mass ratio 1:3 in the first step
Conjunction obtains mixed-powder, and the reaction temperature of pyroreaction is 1000 DEG C, reaction time 60min；The argon flow is
130sccm, oxygen flow 13sccm.Cavity air pressure is 1Pa when magnetic control sputtering device sputters in second step, and argon flow is
30sccm, nitrogen flow 5sccm, sputtering power 150W, sputtering time 30min.The sputtering of third step intermediate ion sputter
When sputtering power be 80W, cavity air pressure be 3Pa, sputtering time 5min, obtained ZnO-WS2CdS core shell nanometer stick array
Pattern is similar to Example 1.
Embodiment 6: method is with embodiment 1, the difference is that the reaction temperature of first step high temperature reaction is 1100 DEG C, reaction
Time is 10min；The argon flow is 180sccm, oxygen flow 18sccm.Chamber when magnetic control sputtering device sputters in second step
Body air pressure is 4Pa, argon flow 50sccm, nitrogen flow 10sccm, sputtering power 80W, sputtering time 5min.The
Sputtering power is 120W when three step intermediate ion sputters sputter, and cavity air pressure is 1.6Pa, and sputtering time 15min is obtained
ZnO-WS2CdS core shell nanometer stick array pattern is similar to Example 1.
Comparative example 1: method is with embodiment 1, the difference is that the ZnO nano-rod array of only first step preparation, it is seen that light produces
Hydrogen is shown in Fig. 3.
Comparative example 2: method is with embodiment 1, the difference is that the only first step and third step, forms ZnO-CdS photochemical catalyst,
Visible light produces hydrogen and sees Fig. 3.
From figure 3, it can be seen that the present invention is in one layer of WS of magnetron sputtering on ZnO nanorod2Film；In ZnO-WS2Nucleocapsid is received
Magnetron sputtering C dS nano particle on rice stick, forms three-dimensional core-shell nanometer rod array, can absorb ZnO and open up by modification CdS
Width arrives visible light, modifies WS2It effectively improves visible light and produces hydrogen activity, while the evenly dispersed WS of ZnO2And CdS, constitute effective electricity
Son transfer energy level realizes quick carrier separation to improve production hydrogen activity, and the ability that catalysis produces hydrogen has obtained very great Cheng
The raising of degree.
Claims (12)
1. a kind of ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield, which is characterized in that including insulating substrate, described
ZnO nano-rod array is distributed on substrate, the ZnO nano-rod array is made of several ZnO nanorods；Several ZnO receive
Rice stick outer layer is WS2Film forms ZnO-WS2Compound system；The ZnO-WS2The load of compound system outer layer has CdS nanometers
Grain.
2. the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 1, which is characterized in that described
The average diameter of ZnO nanorod is 300-1000nm；The WS2Film Average Thickness is 1-10nm；The CdS nano particle
Average grain diameter is 5-15nm.
3. the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 1, which is characterized in that described
Substrate is Sapphire Substrate.
4. the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 1, which is characterized in that described
ZnO nano-rod array is to be grown on a sapphire substrate by vapour deposition process.
5. the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 4, which is characterized in that described
The specific growing method of ZnO nano-rod array are as follows: ZnO powder and carbon dust are mixed to get mixed-powder according to mass ratio 1:1-3,
And it is put into quartzy bottom of the tube；It regard Sapphire Substrate stripping and slicing, cleaning as growth substrate；Mixed-powder and Sapphire Substrate are put into
In quartz ampoule open at one end, will quartz ampoule level be pushed into tube furnace in, vacuumize then pass to 130-180sccm argon gas and
13-18sccm oxygen carries out pyroreaction, and temperature is 1000-1200 DEG C, reaction time 10-60min, and reaction terminates to generate
ZnO nano-rod array.
6. the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 1, which is characterized in that described
WS2Film is that ZnO nanorod outer layer is carried on by sputtering mode, and the equipment used that sputters is magnetic control sputtering device, sputtering
Target is WS2Target, specification are 60 × 3mm, and cavity air pressure is 1-4Pa, argon flow 30-50sccm, nitrogen flow 5-
10sccm, sputtering power 80-150W, sputtering time 5-30min.
7. the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 1, which is characterized in that described
CdS nano particle is carried on ZnO-WS by sputtering mode2Compound system outer layer, the equipment used that sputters is magnetron sputtering
Instrument, sputtering target material are CdS target, and specification is 60 × 3mm, and cavity air pressure is 1-4Pa, argon flow 30-50sccm, nitrogen stream
Amount is 5-10sccm, sputtering power 80-150W, sputtering time 5-30min.
8. a kind of preparation side of the ZnO core-shell nanometer rod array photo catalysis agent of any highly effective hydrogen yield as described in claim 1-7
Method, which comprises the following steps:
(1) vapour deposition process growing ZnO nanorod arrays are used on an insulating substrate；
(2) one layer of WS is sputtered in the ZnO nano-rod array that step (1) obtains2Film forms ZnO-WS2Compound system；
(3) ZnO-WS in the compound system that step (2) obtains2Upper sputtering CdS nano particle forms ZnO-WS2- CdS is compound
System.
9. the preparation method of the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 8, feature
It is in step (1), the growing method of the ZnO nano-rod array is as follows: by ZnO powder and carbon dust according to mass ratio 1:1-
3 are mixed to get mixed-powder, and are put into quartzy bottom of the tube；It regard Sapphire Substrate stripping and slicing, cleaning as growth substrate；By mixed powder
End and Sapphire Substrate are put into quartz ampoule open at one end, and quartz ampoule level is pushed into tube furnace, vacuumizes and then passes to
130-180sccm argon gas and 13-18sccm oxygen carry out pyroreaction, and temperature is 1000-1200 DEG C, reaction time 10-
60min, reaction terminate to generate ZnO nano-rod array.
10. the preparation method of the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 8, special
It levies and is in step (2), the WS2Film specific is the preparation method is as follows: the equipment used is magnetic control sputtering device, sputtering target material
For WS2Target, specification are 60 × 3mm, and cavity air pressure is 1-4Pa, argon flow 30-50sccm, nitrogen flow 5-
10sccm, sputtering power 80-150W, sputtering time 5-30min.
11. the preparation method of the ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield according to claim 8, special
Sign is in step (3) that the CdS nano particle is carried on ZnO-WS by sputtering mode2Compound system outer layer, sputtering use
Equipment be magnetic control sputtering device, sputtering target material is CdS target, and specification is 60 × 3mm, and cavity air pressure is 1-4Pa, and argon flow is
30-50sccm, nitrogen flow 5-10sccm, sputtering power 80-150W, sputtering time 5-30min.
12. a kind of ZnO core-shell nanometer rod array photo catalysis agent of highly effective hydrogen yield any described in claim 1-7 is used for
Hydrogen is produced under light.
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