CN106622293A - Preparation method of H-TiO2/CdS/Cu(2-x)S nanoribbon - Google Patents
Preparation method of H-TiO2/CdS/Cu(2-x)S nanoribbon Download PDFInfo
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- CN106622293A CN106622293A CN201611253917.8A CN201611253917A CN106622293A CN 106622293 A CN106622293 A CN 106622293A CN 201611253917 A CN201611253917 A CN 201611253917A CN 106622293 A CN106622293 A CN 106622293A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002074 nanoribbon Substances 0.000 title abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002114 nanocomposite Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 84
- 239000002127 nanobelt Substances 0.000 claims description 81
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- -1 hydrogen Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000002105 nanoparticle Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000005234 chemical deposition Methods 0.000 abstract 1
- 230000004298 light response Effects 0.000 abstract 1
- 238000006303 photolysis reaction Methods 0.000 abstract 1
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 37
- 239000011734 sodium Substances 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 210000000554 iris Anatomy 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 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
- 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
- B01J27/04—Sulfides
-
- B01J35/39—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a preparation method of an H-TiO2/CdS/Cu(2-x)S nanoribbon, relates to a preparation method of a semiconductor composite and aims to solve the technical problems that existing catalysts have lower solar energy conversion rate and higher cost. The method comprises steps as follows: firstly, a TiO2 nanoribbon is subjected to acid corrosion and reducing atmosphere treatment, and an H-TiO2 nanoribbon with a rough surface is obtained; CdS nanoparticles are modified on the surface of the H-TiO2 nanoribbon with a chemical deposition method, and an H-TiO2/CdS nanocomposite is obtained; finally, part of Cd<2+> is reduced with Cu<+> with an ion exchange method, and an H-TiO2/CdS/Cu(2-x)S nanoribbon catalyst is obtained. The catalyst has good light response to visible light and near infrared areas and can be used in a reaction for producing hydrogen from water through photolysis.
Description
Technical field
The present invention relates to a kind of preparation method of semiconductor composite.
Background technology
With the continuous development of society, in prehistoric formation, the Fossil fuel of centuries, such as coal, natural gas and stone are bred
The oily non-renewable energy resources for waiting these to play an important role in human lives, are reduced constantly, or even be on the verge of exhaustion.Together
When these Fossil fuels burning use during, the air such as many nitrogen oxides, oxysulfide and oxycarbide can be discharged
Pollutant, make global climate change, and drastically influence the health problem of the mankind.Therefore, find renewable, cleaning energy
Source, into the tasks and missions that the world today is extremely urgent.Substantial amounts of hydrogen is produced by photocatalytic water splitting, was catalyzed at this
Cheng Zhong, relates only to the conversion between proton, energy and water, does not produce any by-product and pollutant.Therefore, light is urged
Change process for energy and environment in terms of be made that greatly contribution.And catalyst is prepared, sunlight is effectively absorbed, promotes water
Resolve into for the task with challenge.Solar spectral include only accounting for full spectrum 6.8% ultraviolet spectra (less than 400nm),
38.9% visible light (400-700nm), the infrared spectrum (760-3000nm) for also having 54.3%.Can from the distribution of wave spectrum
To find out, stable catalyst active, inexpensive under development visible ray, effective is one and significantly works.But, mesh
The composite that front various quasiconductors combine, it is impossible to sufficiently using solar spectral, most of catalyst rely on noble metal
Deng as promoter, so that preparation cost is higher.And can absorb entirely if designing and synthesizing one kind in photocatalysis field
The catalyst of wave spectrum, for photocatalysis field, would is that a new breakthrough again.
The content of the invention
The present invention is to solve relatively low to solar energy conversion ratio, the relatively costly technical problem of existing catalyst, and carry
For a kind of H-TiO2/CdS/Cu2-xThe preparation method of S nano belt.
The H-TiO of the present invention2/CdS/Cu2-xThe preparation method of S nano belt, is carried out according to the following steps：
First, nano titanium oxide is scattered in NaOH solution, after ultrasound is uniform, is transferred to ptfe autoclave
In, 48～60h is kept at 160～180 DEG C；After being cooled to room temperature, Na is obtained2Ti3O7Powder；By Na2Ti3O7Powder deionization
Water washing is clean, stirs 24h～48h, after deionized water is cleaned up, by the H for obtaining in being then added to HCl solution2Ti3O7
White powder and H2SO4Solution is put in ptfe autoclave together, keeps 12～24h at 80～100 DEG C；Finally, will obtain
After the product deionized water for obtaining and washes of absolute alcohol are dried, 2～6h are calcined at 400～600 DEG C in being placed on Muffle furnace, obtained
TiO with rough surface2Nano belt；
2nd, the TiO of the rough surface that step one is obtained2Nano belt in the atmosphere of nitrogen and the mixed gas of hydrogen,
It is warming up to 400～600 DEG C and is incubated 4～6h, obtains H-TiO2Nano belt；
3rd, the H-TiO that step 2 is obtained2Nano belt is put into Cd (NO3)2After 30～60min is stirred in solution, centrifugation is washed
Wash, then again by H-TiO2Nano belt is put into Na230～60min, centrifuge washing are stirred in S solution；Cd is used repeatedly so
(NO3)2、Na2After the process repeatedly of S solution, after deionized water and washing with alcohol drying, H-TiO is obtained2The nano combined materials of/CdS
Material；
4th, the H-TiO that step 3 is obtained2Then/CdS nano composite material ultrasonic disperses will in toluene solution
[MeCN]4CuPF6Methanol solution instill H-TiO2In the toluene solution of/CdS nano composite materials, 15～30min is stirred, used
After methanol washing is dried, H-TiO is obtained2/CdS/Cu2-xS nano belt.
The H-TiO that the present invention is processed with acid corrosion and reducing atmosphere2, used as material of main part, cadmium nitrate is used as cadmium for nano belt
Source, sodium sulfide as sulphur source, with the method for chemical bath deposition in H-TiO2CdS nanoparticles are modified in nano belt, H- is obtained
TiO2/ CdS nano composite materials, the method for recycling ion exchange, use Cu+Aliquot replacement Cd2+, it is possible to obtain catalytic performance
Excellent ternary heterojunction structure catalyst.
The H-TiO that the present invention is obtained2/CdS/Cu2-xS nano belt, has good photoresponse to solar spectral, to it is ultraviolet,
It can be seen that and the light of near infrared region have well absorption.And the energy band between three kinds of quasiconductors staggeredly preferably promotes electricity
Son and the separation in hole, when being allowed to the catalyst as Photocatalyzed Hydrogen Production, in the condition that there is no the promoters such as noble metal
Under, hydrogen-producing speed can reach 261.54 μm of olg-1·h-1.And the catalyst of this ternary heterojunction structure has good
Reusing, after five experiments are repeated, hydrogen-producing speed can still reach 210.63 μm of olg-1·h-1。
This material under conditions of no precious metal material is as promoter takes full advantage of sunlight, increased too
Positive transformation of energy utilization rate, promotes the separation in light induced electron and hole, reduces reaction cost, is to prepare with efficient
Catalyst provides new approaches.
Description of the drawings
Fig. 1 be test 1 in prepare without H2SO4The smooth TiO for processing2The scanning electron microscope (SEM) of nano belt
Figure；
Fig. 2 be test 1 in without H2SO4The smooth TiO for processing2The low range scanning electron microscope (SEM) of nano belt
Figure；
Fig. 3 is to test the coarse H-TiO prepared in 12Scanning electron microscope (SEM) figure of nano belt；
Fig. 4 is to test the 1 coarse H-TiO for preparing2Transmission electron microscope (TEM) figure of nano belt；
Fig. 5 is to test 1 H-TiO for preparing2Transmission electron microscope (TEM) figure of/CdS nano composite materials；
Fig. 6 is to test 1 H-TiO for preparing2The granularmetric analyses figure of/CdS nano composite materials；
Fig. 7 is to test 1 H-TiO for preparing2/CdS/Cu2-xTransmission electron microscope (TEM) figure of S nano belt；
Fig. 8 is to test 1 H-TiO for preparing2/CdS/Cu2-xHigh power transmission electron microscope (HRTEM) figure of S nano belt；
Fig. 9 is to test 1 H-TiO for preparing2/CdS/Cu2-xAngle of elevation annular dark-scanning transmission the charge pattern of S nano belt
Distribution diagram of element；
Figure 10 is to test 1 H-TiO for preparing2/CdS/Cu2-xThe x-ray photoelectron energy spectrum diagram of S nano belt；
Figure 11 is to test 1 H-TiO for preparing2/CdS/Cu2-xThe XRD spectra of S nano belt；
Figure 12 is to test 1 H-TiO for preparing2/CdS/Cu2-xThe UV-Vis-NIR spectrograms of S nano belt；
Figure 13 is to test 1 H-TiO for preparing2/CdS/Cu2-xThe hydrogen-producing speed contrast collection of illustrative plates of S nano belt；
Figure 14 is to test 1 H-TiO for preparing2/CdS/Cu2-xHydrogen-producing speed collection of illustrative plates after the recycling of S nano belt.
Specific embodiment
Specific embodiment one：The H-TiO of present embodiment2/CdS/Cu2-xThe preparation method of S nano belt, by following step
Suddenly carry out：
First, nano titanium oxide is scattered in NaOH solution, after ultrasound is uniform, is transferred to ptfe autoclave
In, 48～60h is kept at 160～180 DEG C；After being cooled to room temperature, Na is obtained2Ti3O7Powder；By Na2Ti3O7Powder deionization
Water washing is clean, stirs 24h～48h, after deionized water is cleaned up, by the H for obtaining in being then added to HCl solution2Ti3O7
White powder and H2SO4Solution is put in ptfe autoclave together, keeps 12～24h at 80～100 DEG C；Finally, will obtain
After the product deionized water for obtaining and washes of absolute alcohol are dried, 2～6h are calcined at 400～600 DEG C in being placed on Muffle furnace, obtained
TiO with rough surface2Nano belt；
2nd, the TiO of the rough surface that step one is obtained2Nano belt in the atmosphere of nitrogen and the mixed gas of hydrogen,
It is warming up to 400～600 DEG C and is incubated 4～6h, obtains H-TiO2Nano belt；
3rd, the H-TiO that step 2 is obtained2Nano belt is put into Cd (NO3)2After 30～60min is stirred in solution, centrifugation is washed
Wash, then again by H-TiO2Nano belt is put into Na230～60min, centrifuge washing are stirred in S solution；Cd is used repeatedly so
(NO3)2、Na2After the process repeatedly of S solution, after deionized water and washing with alcohol drying, H-TiO is obtained2The nano combined materials of/CdS
Material；
4th, the H-TiO that step 3 is obtained2Then/CdS nano composite material ultrasonic disperses will in toluene solution
[MeCN]4CuPF6Methanol solution instill H-TiO2In the toluene solution of/CdS nano composite materials, 15～30min is stirred, used
After methanol washing is dried, H-TiO is obtained2/CdS/Cu2-xS nano belt.
Specific embodiment two：Present embodiment from step one unlike specific embodiment one NaOH solution it is dense
Spend for 5～10mol/L；Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment and HCl solution in step one unlike specific embodiment one or two
Concentration be 0.1～0.5mol/L；Other are identical with specific embodiment one or two.
Specific embodiment four：In step one unlike one of present embodiment and specific embodiment one to three
H2SO4The concentration of solution is 0.02～0.05mol/L；Other are identical with one of specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four described in step 2
Nitrogen and hydrogen mixed gas in H2Account for the 5%～10% of mixed gas volume；Other and specific embodiment one to four
One of it is identical.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five described in step 2
Heating rate be 2～5 DEG C/min；Other are identical with one of specific embodiment one to five.
Specific embodiment seven：Cd in step 3 unlike one of present embodiment and specific embodiment one to six
(NO3)2The concentration of solution is 0.05～0.1mol/L；Other are identical with one of specific embodiment one to six.
Specific embodiment eight：Na in step 3 unlike one of present embodiment and specific embodiment one to seven2S
The concentration of Solutions Solution is 0.05～0.1mol/L；Other are identical with one of specific embodiment one to seven.
Specific embodiment nine：In step 3 unlike one of present embodiment and specific embodiment one to eight repeatedly
With Cd (NO3)2、Na2S solution number of processing is 4～5 times；Other are identical with one of specific embodiment one to eight.
Specific embodiment ten：In step 4 unlike one of present embodiment and specific embodiment one to nine
[MeCN]4CuPF6The concentration of methanol solution is 2.5～10mg/mL；Other are identical with one of specific embodiment one to nine.
With following verification experimental verification beneficial effects of the present invention：
Test 1：The H-TiO of this test2/CdS/Cu2-xThe preparation method of S nano belt, is carried out according to the following steps：
First, 0.5g nano titanium oxide P25 are scattered in the NaOH solution that 20mL concentration is 5mol/L, treat ultrasonic disperse
After uniform, be transferred in ptfe autoclave, 48h is kept at 180 DEG C；After being cooled to room temperature, by the Na for obtaining2Ti3O7Powder
End is washed with deionized totally, then in HCl solution of the concentration for 0.5mol/L stirs 24h, and deionized water is cleaned up
Afterwards, by the H for obtaining2Ti3O7White powder and the H that 20mL concentration is 0.05mol/L2SO4It is anti-that solution is put into politef together
In answering kettle, 12h is kept at 100 DEG C；Finally, after the product deionized water for obtaining and washes of absolute alcohol being dried, it is placed on horse
Not 2h is calcined at 500 DEG C in stove, obtain the TiO with rough surface2Nano belt；
2nd, the TiO of the rough surface that step one is obtained2Nano belt is in H2Mass percent be 5% N2With H2It is mixed
Close in the atmosphere of gas, 600 DEG C are warming up to the heating rate of 2 DEG C/min and are incubated 4h, obtain the H-TiO of black2Nano belt；
3rd, the 200mg H-TiO for step 2 being obtained2Nano belt is put into the Cd (NO that 50mL concentration is 0.1mol/L3)2It is molten
In liquid, after stirring 30min, centrifuge washing, then again by H-TiO2Nano belt is put into the Na that 50mL concentration is 0.1mol/L2S solution
In, stir 30min, centrifuge washing；Cd (NO are used repeatedly so3)2、Na2After S solution processes 4 times, deionized water and ethanol are washed
Wash after being dried, obtain flaxen H-TiO2/ CdS nano composite materials；
4th, the 100mg H-TiO for step 3 being obtained2/ CdS nano composite materials ultrasonic disperse is in 20mL toluene solutions
It is stand-by, then by [MeCN] of 50mg4CuPF6[MeCN] is obtained in being dissolved in 10mL methanol4CuPF6Methanol solution, by [MeCN]4CuPF6Methanol solution is dropwise added dropwise to H-TiO2In/CdS nano composite material toluene solutions, 15min is stirred, 3 is washed with methanol
It is secondary, after being dried, obtain H-TiO2/CdS/Cu2-xS nano belt catalyst.
TiO prepared by this test Jing steps one2Scanning electron microscope (SEM) figure of nano belt as depicted in figs. 1 and 2,
TiO be can be seen that from Fig. 1 and Fig. 22The width of nano belt is 100-200nm or so, and length is beyond 50 μm.
The H-TiO of the black that this test Jing step 2 is obtained2The SEM of nano belt is schemed as shown in figure 3, transmission electron microscope
(TEM) figure is as shown in figure 4, from figs. 3 and 4 it can be seen that after acid treatment and reducing atmosphere are processed, TiO2The table of nano belt
Face becomes very coarse, and the thus attachment for next step CdS nanoparticle provides good substrate while material can be increased
Oxygen vacancies density, so as to increase the response in visible region.
The H-TiO that this test procedure three is obtained2The TEM photos of/CdS nano composite materials are as shown in figure 5, H-TiO2/CdS
The granularmetric analyses figure of nano composite material as shown in fig. 6, knowable to Fig. 5 and Fig. 6, through the method for chemical bath deposition, preparation
CdS nanoparticle size is 3-5nm, and is evenly distributed in H-TiO2In nano belt.
The H-TiO that this test Jing step 4 is obtained2/CdS/Cu2-xThe TEM of S nano belt is schemed as shown in fig. 7, can from Fig. 7
To find out, Cu+Part replaces Cd2+, same is evenly distributed on H-TiO2In nano belt.H-TiO2/CdS/Cu2-xS nano belt
HRTEM photos are as shown in figure 8, from figure 8, it is seen that TiO2Interplanar distance be 0.352nm, correspond to its (101) crystal face；
The interplanar distance of CdS is 0.336nm, corresponds to its (111) crystal face.It is CdS nano-particle that in figure, black line irises out the part come, in vain
It is the unbodied Cu being looped around around CdS nano-particle that colo(u)r streak irises out the part come2-xS nanoparticles.
The H-TiO that this test Jing step 4 is obtained2/CdS/Cu2-xThe angle of elevation annular dark of S nano belt-scanning transmission electricity
In son picture, scanning transmission microphotograph is as shown in figure 9, from fig. 9, it can be seen that five kinds of elements of Ti, O, Cd, Cu and S are uniformly distributed
In H-TiO2In nano belt, while this also illustrates that H-TiO has successfully been prepared in this test2/CdS/Cu2-xS nano belt.
In order to further analyze the existence form of sample, the H-TiO that this test Jing step 4 is obtained is analyzed2/CdS/
Cu2-xThe XPS collection of illustrative plates of S nano belt as shown in Figure 10, is composed in (a) as can be seen that comprising Ti, O, Cd, Cu in the material entirely from Figure 10
With five kinds of elements of S.As can be seen that the energy level of 405.8eV and 412.5eV corresponds to Cd respectively in the 3d tracks of Cd elements from (b)
3d5/2And 3d3/2；From (c) it can be seen that the energy level of 932.5eV and 952.1eV corresponds to Cu's respectively in the 2p tracks of Cu elements
2p3/2And 2p1/2；The 2p track of S element is belonged to positioned at the peak at 162.1eV from (d), and being located at the peak at 169.2eV is then
Due to S2-Partial oxidation caused by.
Figure 11 is the prepared H-TiO of this test2、H-TiO2/ CdS and H-TiO2/CdS/Cu2-xThe XRD figure of S nano belt
Spectrum, it can be seen from fig. 11 that H-TiO2The main crystal formation of nano belt is anatase, correspondence PDF card 21-1272, also few
The titanium dioxide of the monoclinic form of amount is present, correspondence PDF card 46-1238；From H-TiO2The XRD figure of/CdS nano composite materials
As can be seen that the crystal formation of CdS nanoparticles is cubic system, correspondence PDF card 10-0454, wherein positioned at 2 θ be 26.5 °,
Peak at 43.9 ° and 52.1 ° correspond to (111), (220) and (311) crystal face of CdS nanoparticles respectively.And in XRD figure
In, no discovery belongs to Cu2-xThe characteristic peak of S nanoparticles, this also further demonstrate that we pass through ion-exchange process system
Standby Cu2-xS nanoparticles are present in unbodied mode.
Again preparing material TiO as a comparison2/ CdS nano composite materials and TiO2/CdS/Cu2-xS nano belt, its system
Preparation Method is as follows：0.5g nano titanium oxide P25 are scattered in the NaOH solution that 20mL concentration is 5mol/L, ultrasonic disperse is treated
After uniform, be transferred in ptfe autoclave, 48h is kept at 180 DEG C；After being cooled to room temperature, by the Na for obtaining2Ti3O7Powder
End is washed with deionized totally, then in HCl solution of the concentration for 0.5mol/L stirs 24h, and deionized water is cleaned up
Afterwards, 2h is calcined at 500 DEG C in being placed on Muffle furnace, obtain TiO2Nano belt；200mg TiO2Nano belt is put into 50mL concentration
Cd (the NO of 0.1mol/L3)2In solution, after stirring 30min, centrifuge washing, then again by TiO2Nano belt is put into 50mL concentration
The Na of 0.1mol/L2In S solution, 30min, centrifuge washing are stirred；Cd (NO are used repeatedly so3)2、Na2After S solution processes 4 times,
After deionized water and washing with alcohol are dried, TiO is obtained2/ CdS nano composite materials.Again by 100mg TiO2/ CdS is nano combined
Material ultrasonic disperse is stand-by in 20mL toluene solutions, then by [MeCN] of 50mg4CuPF6Obtain in being dissolved in 10mL methanol
[MeCN]4CuPF6Methanol solution, by [MeCN]4CuPF6Methanol solution is dropwise added dropwise to TiO2/ CdS nano composite material toluene is molten
In liquid, 15min is stirred, is washed with methanol 3 times, obtained after being dried.
TiO prepared by contrast test2/ CdS and TiO2/CdS/Cu2-xH-TiO prepared by S, this test Jing step 32/
H-TiO prepared by CdS and this test Jing step 42/CdS/Cu2-xTetra- kinds of samples of S carry out absorption spectrum test, the absorption for obtaining
Spectrogram is as shown in figure 12.It can be recognized from fig. 12 that TiO2/ CdS and H-TiO2The absorption region of/CdS between 400-520nm,
The addition of CdS nanoparticles is this demonstrated, response of the material in visible region is promoted.Because absorbing with phasmon
Cu2-xThe presence of S nanoparticles so that absorption of the material to solar spectral reaches near infrared region.Additionally, can by collection of illustrative plates
To find out, with H-TiO2Material for substrate has higher absorbability, and this is due to hydrogenating later H-TiO2Interface disorder
The reason for existing with oxygen vacancies.
The TiO that just prepared by contrast test2/ CdS and TiO2/CdS/Cu2-xH-TiO prepared by S, this test Jing step 32/
H-TiO prepared by CdS and this test Jing step 42/CdS/Cu2-xTetra- kinds of samples of S are applied to the reaction of photocatalytic hydrogen production by water decomposition
In the hydrogen-producing speed figure of different materials that obtains as shown in figure 13, H-TiO as can be seen from Figure 132/CdS/Cu2-xS nano belt catalyst
There is good catalytic performance, hydrogen-producing speed can reach 261.51 μm of olg-1·h-1。
Figure 14 is the H-TiO for preparing this test2/CdS/Cu2-xS is applied in the reaction of photocatalytic hydrogen production by water decomposition, weight
Test the data result for obtaining multiple five times, can as seen from the figure, the catalyst has good catalytic performance and stable circulation
Property, after five experiments are repeated, hydrogen-producing speed is still very high, can reach 210.63 μm of olg-1-h-1。
Can be drawn according to the characterization result of product prepared by above-mentioned test 1, be prepared for having using this success of the test
High solar transformation efficiency, and the H-TiO of low cost2/CdS/Cu2-xS nano belt.The catalyst is in photocatalytic water splitting
In experimental applications, with excellent catalytic performance.
Test 2：The H-TiO of this test2/CdS/Cu2-xThe preparation method of S nano belt, is carried out according to the following steps：
First, 0.3g nano titanium oxide P25 are scattered in the NaOH solution that 20mL concentration is 8mol/L, treat ultrasonic disperse
After uniform, be transferred in ptfe autoclave, 48h is kept at 170 DEG C；After being cooled to room temperature, by the Na for obtaining2Ti3O7Powder
End is washed with deionized totally, then in HCl solution of the concentration for 0.4mol/L stirs 24h, and deionized water is cleaned up
Afterwards, by the H for obtaining2Ti3O7White powder and the H that 20mL concentration is 0.04mol/L2SO4It is anti-that solution is put into politef together
In answering kettle, 12h is kept at 90 DEG C；Finally, after the product deionized water for obtaining and washes of absolute alcohol being dried, it is placed on Muffle
2h is calcined at 600 DEG C in stove, the TiO with rough surface is obtained2Nano belt；
2nd, the TiO of the rough surface that step one is obtained2Nano belt is in H2Mass percent be 5% N2With H2It is mixed
Close in the atmosphere of gas, 600 DEG C are warming up to the heating rate of 2 DEG C/min and are incubated 4h, obtain the H-TiO of black2Nano belt；
3rd, the 150mg H-TiO for step 2 being obtained2Nano belt is put into the Cd (NO that 50mL concentration is 0.05mol/L3)2It is molten
In liquid, after stirring 30min, centrifuge washing, then again by H-TiO2Nano belt is put into the Na that 50mL concentration is 0.05mol/L2S is molten
In liquid, 30min, centrifuge washing are stirred；Cd (NO are used repeatedly so3)2、Na2After S solution processes 4 times, deionized water and ethanol
After washing is dried, flaxen H-TiO is obtained2/ CdS nano composite materials；
4th, the 50mg H-TiO for step 3 being obtained2/ CdS nano composite materials ultrasonic disperse is in 20mL toluene solutions
It is stand-by, then by [MeCN] of 20mg4CuPF6[MeCN] is obtained in being dissolved in 10mL methanol4CuPF6Methanol solution, by [MeCN]4CuPF6Methanol solution is dropwise added dropwise to H-TiO2In/CdS nano composite material toluene solutions, 15min is stirred, 3 is washed with methanol
It is secondary, after being dried, obtain H-TiO2/CdS/Cu2-xS nano belt catalyst.
The H-TiO that this test is obtained2/CdS/Cu2-xS nano belt catalyst is applied to the reaction of photocatalytic hydrogen production by water decomposition
In, its hydrogen-producing speed is 240.18 μm of olg-1·h-1。
Claims (10)
1. a kind of H-TiO2/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that the method is carried out according to the following steps：
First, nano titanium oxide is scattered in NaOH solution, after ultrasound is uniform, is transferred in ptfe autoclave,
48～60h is kept at 160～180 DEG C；After being cooled to room temperature, Na is obtained2Ti3O7Powder；By Na2Ti3O7Powder deionized water
Washes clean, stirs 24h～48h in being then added to HCl solution, after deionized water is cleaned up, by the H for obtaining2Ti3O7In vain
Color powder and H2SO4Solution is put in ptfe autoclave together, keeps 12～24h at 80～100 DEG C；Finally, will obtain
Product deionized water and after washes of absolute alcohol is dried, be placed in Muffle furnace and calcine 2～6h at 400～600 DEG C, had
There is the TiO of rough surface2Nano belt；
2nd, the TiO of the rough surface that step one is obtained2Nano belt is warming up in atmosphere of the nitrogen with the mixed gas of hydrogen
400～600 DEG C and 4～6h is incubated, obtains H-TiO2Nano belt；
3rd, the H-TiO that step 2 is obtained2Nano belt is put into Cd (NO3)2After 30～60min is stirred in solution, centrifuge washing, so
Afterwards again by H-TiO2Nano belt is put into Na230～60min, centrifuge washing are stirred in S solution；Cd (NO are used repeatedly so3)2、Na2S
After solution process repeatedly, after deionized water and washing with alcohol drying, H-TiO is obtained2/ CdS nano composite materials；
4th, the H-TiO that step 3 is obtained2/ CdS nano composite material ultrasonic disperses in toluene solution, then by [MeCN]4CuPF6Methanol solution instill H-TiO2In the toluene solution of/CdS nano composite materials, 15～30min is stirred, is washed with methanol
Wash after being dried, obtain H-TiO2/CdS/Cu2-xS nano belt.
2. a kind of H-TiO according to claim 12/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step one
The concentration of middle NaOH solution is 5～10mol/L.
3. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
In rapid one, the concentration of HCl solution is 0.1～0.5mol/L.
4. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
H in rapid one2SO4The concentration of solution is 0.02～0.05mol/L.
5. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
Nitrogen described in rapid two and H in the mixed gas of hydrogen2Account for the 5%～10% of mixed gas volume.
6. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
Heating rate described in rapid two is 2～5 DEG C/min.
7. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
Cd (NO in rapid three3)2The concentration of solution is 0.05～0.1mol/L.
8. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
Na in rapid three2The concentration of S Solutions Solutions is 0.05～0.1mol/L.
9. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
Cd (NO are used repeatedly in rapid three3)2、Na2S solution number of processing is 4～5 times.
10. a kind of H-TiO according to claim 1 and 22/CdS/Cu2-xThe preparation method of S nano belt, it is characterised in that step
In rapid four [MeCN]4CuPF6The concentration of methanol solution is 2.5～10mg/mL.
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