CN104857942A - Cadmium sulfide sensitization hydrogenation branched titanium dioxide nanorod array membrane and light catalyst - Google Patents

Cadmium sulfide sensitization hydrogenation branched titanium dioxide nanorod array membrane and light catalyst Download PDF

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CN104857942A
CN104857942A CN201510206125.4A CN201510206125A CN104857942A CN 104857942 A CN104857942 A CN 104857942A CN 201510206125 A CN201510206125 A CN 201510206125A CN 104857942 A CN104857942 A CN 104857942A
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branched
hydrogenation
cadmium sulfide
nanorod array
array membrane
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张声森
方岳平
晏洁
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South China Agricultural University
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South China Agricultural University
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    • 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

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Abstract

The invention belongs to the photocatalysis technological field and discloses a cadmium sulfide sensitization hydrogenation branched titanium dioxide nanorod array membrane, a production method of the nanorod array membrane, a light catalyst produced based on the nanorod array membrane and an application in visible light catalysis decomposition of aquatic hydrogen. The array membrane is produced through the method including the steps of submerging conductive glass in a tetrabutyl titanate and hydrochloric acid aqueous solution with the conductive glass serving as a substrate to be subjected to heating reaction, submerging the mixture into a TiCl3 hydrochloric acid solution to obtain the branched titanium dioxide nanorod array membrane; hydrogenating the titanium dioxide nanorod array membrane in the hydrogen atmosphere; loading cadmium sulfide nanometer particles through a chemical sedimentation method to obtain the cadmium sulfide sensitization hydrogenation branched titanium dioxide nanorod array membrane. The invention further provides an array membrane based light catalyst. The array membrane has high aquatic hydrogen visible light catalytic decomposition cavity, and the produced light catalyst is outstanding in performance, good in stability and capable of being reused conveniently.

Description

The branched titanic oxide nanorod array film of cadmium sulfide sensitization hydrogenation and photocatalyst
Technical field
The invention belongs to photocatalysis technology field, branched titanic oxide nanorod array film of particularly a kind of sensitized by cadmium sulfide nanoparticles hydrogenation and preparation method thereof and based on its photocatalyst prepared and the application of to decompose at visible light catalytic in aquatic products hydrogen.
Background technology
Along with the development of society, people more and more pay close attention to for the energy and ecological environment, and catalysis material has huge potentiality in solution energy shortage and environmental pollution.The light hydrogen production by water decomposition practical technique of efficiency utilization sunshine is the ultimate energy dream that people pursue always, become one of focus of various countries scientist research, but the high-activity photocatalyst obtaining efficiency utilization sunshine remains a long-term and challenge for arduousness.Among many catalysis materials, titanium dioxide (TiO 2) because have suitable band gap and can band edge position, cheap, environmental protection, the plurality of advantages such as photocatalysis efficiency high (under ultraviolet light) and stable performance, be considered to one of the most promising catalysis material in future always.
California, USA university Chen XB in 2011 etc. (Science, 331 (2011), 746) are by TiO 2nanocrystalline at 200 DEG C, H under 20bar 2middle process is after 5 days, the TiO of white 2become black, the TiO of this black 2not only increase the absorption in visible-range, also greatly strengthen the absorption of ultraviolet light, under sunshine, photodissociation aquatic products hydrogen and the photodegradative performance of organic matter are obtained for large increase, and stability is fine.Subsequently, at the one dimension TiO of tin oxide (FTO) the upper preparation hydrogenation of Fluorin doped 2nano-stick array membrane contains suitable oxygen vacancies and Ti because of it 3+and there is good photocatalysis performance and electric conductivity (Nano Letter, 11 (2011), 3026).Although hydrogenation TiO 2strengthen greatly the absorption of visible ray, but do not bring the visible light activity obviously strengthened, this is the key of restriction solar energy photocatalytic technical application.
Cadmium sulfide (CdS) has suitable band gap (2.4eV) because of it and can be with position, can be applicable to visible light photocatalysis and decompose aquatic products hydrogen, but pure CdS causes its catalytic performance not high because light induced electron and hole are easy to compound; And TiO 2after compound, because it can be with position and TiO 2coupling, its photocatalysis voltinism can be greatly improved.But light induced electron transmission performance is in the film not high, it can not be used for pure photocatalysis Decomposition aquatic products hydrogen.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is the branched titanic oxide nanorod array film providing a kind of sensitized by cadmium sulfide nanoparticles hydrogenation.
Another object of the present invention is the preparation method of the branched titanic oxide nanorod array film of the sensitized by cadmium sulfide nanoparticles hydrogenation providing a kind of said method to prepare.
Still a further object of the present invention is the photocatalyst providing a kind of branched titanic oxide nanorod array film based on above-mentioned sensitized by cadmium sulfide nanoparticles hydrogenation.
Still a further object of the present invention is to provide the branched titanic oxide nanorod array film of above-mentioned sensitized by cadmium sulfide nanoparticles hydrogenation to decompose the application in aquatic products hydrogen at visible light catalytic.
Still a further object of the present invention is to provide above-mentioned photocatalyst to decompose the application in aquatic products hydrogen at visible light catalytic.
Object of the present invention is realized by following proposal:
A kind of branched titanium dioxide (TiO of cadmium sulfide (CdS) nanoparticle sensitized hydrogenation 2) nano-stick array membrane, prepared by the method comprised the following steps:
Using electro-conductive glass as substrate, be immersed in the heated in water solution reaction of butyl titanate and hydrochloric acid, then immerse TiCl 3hydrochloric acid solution in, obtain branched TiO 2nano-stick array membrane; Be placed on hydrogenation under atmosphere of hydrogen; Adopt CdS nano particle in chemical deposition load again, obtain the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2nano-stick array membrane.
Described electro-conductive glass refers to FTO electro-conductive glass, ITO electro-conductive glass, metallized glass or metal-oxide film glass etc.
Described butyl titanate and salt aqueous acid are preferably the butyl titanate of 1:50:50 ~ 1:20:20 with volume ratio, concentrated hydrochloric acid and water configuration obtain.In layoutprocedure, preferably first concentrated hydrochloric acid and water mixing and stirring are added butyl titanate again and mix and obtain.
The described condition adding thermal response is 140 ~ 180 DEG C of reaction 4 ~ 8h.
Described immersion TiCl 3hydrochloric acid solution in condition be 70 ~ 90 DEG C soak 0.5 ~ 2h.
Described TiCl 3hydrochloric acid solution in TiCl 3concentration be preferably 0.005 ~ 0.2M.Described immersion TiCl 3hydrochloric acid solution process in, its by chemical bath deposition at TiO 2nano-stick array membrane superficial growth goes out branch structure.Described TiCl 3hydrochloric acid solution in hydrochloric acid be used for preventing TiCl 3be hydrolyzed, its content is about 0.1mL/10mL solution.
Preferably, the condition of described hydrogenation is 250 ~ 450 DEG C of hydrogenation 1 ~ 3h, is more preferably 300 ~ 400 DEG C of hydrogenation 1 ~ 3h.
Described hydrogenation is hydrogenation in the mixed atmosphere of hydrogen and inert gas preferably.The flow velocity of described hydrogen is preferably 20SCCM, and the flow velocity of described inert gas is preferably 80SCCM.
Preferably, CdS nano particle in the load of described employing chemical deposition, by the sulphur source precursor solution of first configuration concentration to be the cadmium source precursor solution of 0.05 ~ 1M and concentration be 0.05 ~ 1M, obtained the branched TiO of cadmium sulfide (CdS) nanoparticle sensitized hydrogenation by the continuous chemical water-bath sedimentation of 3 ~ 15 sensitizations circulation 2nano-stick array membrane.
More particularly by the sulphur source precursor solution of first configuration concentration to be the cadmium source precursor solution of 0.1 ~ 0.8M and concentration be 0.1 ~ 0.8M, obtained the branched TiO of cadmium sulfide (CdS) nanoparticle sensitized hydrogenation by the continuous chemical water-bath sedimentation of 5 ~ 9 sensitizations circulation 2nano-stick array membrane.
Described cadmium source precursor solution can be Cd (NO 3) 2the aqueous solution, CdCl 2the aqueous solution or CdSO 4the aqueous solution, is preferably Cd (NO 3) 2the aqueous solution.
Described sulphur source precursor solution can be Na 2the S aqueous solution, K 2the S aqueous solution or (NH 4) 2the S aqueous solution, is preferably Na 2the S aqueous solution.
The branched TiO of the nanoparticle sensitized hydrogenation of CdS of the present invention 2the rod length of its trunk nanometer rods of nano-stick array membrane is 0.5 ~ 1.8 μm, and excellent footpath is 70 ~ 180nm; Described branch structure is thorn-like, and its length is 10 ~ 100nm.
The branched TiO of the nanoparticle sensitized hydrogenation of CdS of the present invention 2the visible light photocatalysis performance of nano-stick array membrane is enhanced, and can be applicable to visible light catalytic and decomposes in aquatic products hydrogen.
Based on a photocatalyst for the branched titanic oxide nanorod array film of above-mentioned sensitized by cadmium sulfide nanoparticles hydrogenation, obtain by the branched titanic oxide nanorod array film of described sensitized by cadmium sulfide nanoparticles hydrogenation is connected with wire.
Described wire can be Pt, Au or Ag silk, is preferably Pt silk.
The wire connected in above-mentioned photocatalyst plays a role as light induced electron receiver.
Above-mentioned photocatalyst can be applicable to visible light catalytic and decomposes in aquatic products hydrogen.
Mechanism of the present invention and advantage:
The branched TiO of the nanoparticle sensitized hydrogenation of CdS of the present invention 2nano-stick array membrane passes through the design of hydrogenization and branch structure, for light induced electron conduction provides effective transmission path, effectively suppresses the compound of photo-generate electron-hole; Again by CdS sensitization, enhance the visible light photocatalysis performance of film, improve the activity that its visible light photocatalysis decomposes aquatic products hydrogen.Utilize the branched TiO of the nanoparticle sensitized hydrogenation of CdS of the present invention 2nano-stick array membrane connects with wire, obtains excellent performance, good stability, can facilitate reusable photocatalyst.This photocatalyst further increases light induced electron and the hole separative efficiency of CdS, has efficient visible light catalytic decomposition water H2-producing capacity.Preparation process controllability of the present invention is strong, and photocatalysis performance is stablized, reproducible; The method is simple, and without the need to main equipment, economically feasible, is easy to industrialization, produces in hydrogen etc. have broad prospects at sunlight photocatalysis.
Accompanying drawing explanation
Fig. 1 is the photocatalyst structural representation of embodiment 1.
Fig. 2 is field emission scanning electron microscope (FESEM) figure of embodiment 1.Wherein, A is the branched TiO of hydrogenation 2the FESEM figure of nano-stick array membrane; B is the branched TiO of CdS sensitization hydrogenation 2the FESEM figure of nano-stick array membrane.
Fig. 3 is projection Electronic Speculum (TEM) high-resolution projection Electronic Speculum (HRTEM) figure of embodiment 1.A, B and C are the branched TiO of hydrogenation 2tEM and the HRTEM figure of nanometer stick array; D, E and F are the branched TiO of CdS sensitization hydrogenation 2tEM and the HRTEM figure of nano-stick array membrane.
Fig. 4 is ultraviolet-visible light solid diffuse reflection spectrum (DRS) figure of embodiment 1.Wherein, a is the branched TiO of hydrogenation 2nano-stick array membrane; B is the branched TiO of CdS sensitization hydrogenation 2nano-stick array membrane; C is the unhydrided branched TiO of CdS sensitization 2nanometer rods.
Fig. 5 is the visible light photocatalysis hydrogen production by water decomposition activity figure of the photocatalyst of embodiment 1.Wherein, a is the branched TiO of hydrogenation 2the photocatalyst of nanometer stick array film preparation; B is the branched TiO of CdS sensitization hydrogenation 2the photocatalyst of nanometer stick array film preparation; C is the unhydrided branched TiO of CdS sensitization 2photocatalyst prepared by nanometer rods.
Fig. 6 is the photocatalyst photocatalytic hydrogen production by water decomposition rate diagram under visible light of embodiment 1 ~ 7.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) branched TiO 2the preparation of nano-stick array membrane
1. by FTO electro-conductive glass priority ultrasonic 30min in deionized water, acetone and ethanolic solution successively, clean through deionized water, dry up for subsequent use;
2. prepare the precursor solution in titanium source: first mixed with 30mL deionized water by 30mL concentrated hydrochloric acid (mass concentration is 37.5%), stir and add l mL butyl titanate and continue stirring 5 minutes afterwards for 5 minutes, obtain titanium source precursor solution;
3. the conducting surface of FTO electro-conductive glass is placed in reactor obliquely, adds titanium source precursor solution, react 7 hours under 150 DEG C of conditions, deionized water is washed, dry at 80 DEG C, obtains TiO 2nano-stick array membrane.
4. the TiO will prepared 2it is the TiCl of 0.01M that nanometer rods immerses containing 10mL concentration 3in hydrochloric acid solution, wherein content of hydrochloric acid is 0.01mL/10mL solution, and 80 DEG C of constant temperature growth 1h, obtain branched TiO 2nano-stick array membrane.
(2) by branched TiO 2nano-stick array membrane is placed in hydrogen atmosphere hydrogenation, and hydrogen atmosphere is the mist of hydrogen argon gas.The flow velocity of hydrogen is 20SCCM, and the flow velocity of argon gas is 80SCCM, and hydrogenation temperature is 350 DEG C, and hydrogenation time is 2h, obtains the branched TiO of hydrogenation 2nano-stick array membrane.
(3) the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2the preparation of nano-stick array membrane
1. Cd (the NO of 0.5M is prepared 3) 2the aqueous solution, the Na of 0.5M 2the S aqueous solution;
2. with the branched TiO of hydrogenation 2nano-stick array membrane is substrate, is prepared the branched TiO of the nanoparticle sensitized hydrogenation of CdS by the continuous chemical water-bath deposition repeatedly circulated 2nano-stick array membrane;
Single cycle is operating as the branched TiO of hydrogenation 2nano-stick array membrane is immersed in Cd (NO 3) 2in the aqueous solution, 3min afterflush is clean, then puts into Na 2the S aqueous solution, 3min afterflush is clean;
Repetitive cycling operates 7 times, obtains the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2nano-stick array membrane.
(4) with the branched TiO of the obtained nanoparticle sensitized hydrogenation of CdS of step (3) 2nano-stick array membrane is used for visible light photocatalysis and decomposes aquatic products hydrogen, and concrete grammar is: the branched TiO of the nanoparticle sensitized hydrogenation of the CdS prepared 2the photochemical catalyzing experiment of nano-stick array membrane is carried out in internal-circulation type reaction system.4.0cm 2above-mentioned array films connects a Pt silk and is fixed on 80mL containing in the methanol aqueous solution of 5%, with 300W xenon lamp for light source, with UV-400 optical filter the ultraviolet light elimination of below 400nm, and remaining radiation of visible light.The hydrogen produced in experiment is analyzed by online gas-chromatography (GC-14C type, Japan, TCD).Xenon lamp is 10cm from the distance of array films.Structural representation is shown in Fig. 1.
(5) implementation result of the present embodiment: Fig. 2 and Fig. 3 is the branched TiO of hydrogenation prepared by the present embodiment 2the branched TiO of nano-stick array membrane and the nanoparticle sensitized hydrogenation of CdS 2sEM, TEM and HRTEM figure of nano-stick array membrane;
Fig. 4 is the branched TiO of hydrogenation prepared by the present embodiment 2the branched TiO of nano-stick array membrane and the nanoparticle sensitized hydrogenation of CdS 2the comparison diagram of the uv-visible absorption spectra figure of nano-stick array membrane, as seen from the figure, the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2nano-stick array membrane improves greatly in being absorbed with of visible region;
Fig. 5 is the branched TiO of the nanoparticle sensitized hydrogenation of CdS prepared by the present embodiment 2nano-stick array membrane and the unhydrided branched TiO of CdS sensitization 2nano-stick array membrane (, only without hydrogenation, other steps are identical for preparation method) hydrogen production activity comparison diagram under visible light, as seen from the figure, the branched TiO of the nanoparticle sensitized hydrogenation of the CdS utilizing the present embodiment to prepare 2nano-stick array membrane, the speed of release hydrogen is far above the branched TiO not having CdS-loaded hydrogenation 2nano-stick array membrane, the also branched TiO not having hydrogenation of CdS higher than load 2nanometer stick array film catalyst.
Under its visible ray, photocatalytic hydrogen production by water decomposition speed is see Fig. 6.
Embodiment 2
(1) branched TiO 2the preparation of nano-stick array membrane is with embodiment 1.
(2) the branched TiO of hydrogenation 2the preparation of nano-stick array membrane is with embodiment 1.
(3) the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2the preparation of nano-stick array membrane
1. Cd (the NO of 0.1M is prepared 3) 2the aqueous solution, the Na of 0.1M 2the S aqueous solution;
2. with the branched TiO of hydrogenation 2nano-stick array membrane is substrate, is prepared the branched TiO of the nanoparticle sensitized hydrogenation of CdS by the continuous chemical water-bath deposition repeatedly circulated 2nano-stick array membrane;
Single cycle is operating as the branched TiO of hydrogenation 2nano-stick array membrane is immersed in Cd (NO 3) 2in the aqueous solution, 3min afterflush is clean, then puts into Na 2the S aqueous solution, 3min afterflush is clean;
Repetitive cycling operates 9 times, obtains the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2nano-stick array membrane.
The branched TiO of the nanoparticle sensitized hydrogenation of the CdS prepared 2under the visible ray of nano-stick array membrane, photocatalytic hydrogen production by water decomposition speed is see Fig. 6.
Embodiment 3
(1) branched TiO 2the preparation of nano-stick array membrane is with embodiment 1.
(2) the branched TiO of hydrogenation 2the preparation of nano-stick array membrane is with embodiment 1.
(3) the branched TiO of the branched particle sensitization hydrogenation of the nanoparticle sensitized hydrogenation of CdS 2the preparation of nano-stick array membrane
1. Cd (the NO of 0.8M is prepared 3) 2the aqueous solution, the Na of 0.8M 2the S aqueous solution;
2. with the branched TiO of hydrogenation 2nano-stick array membrane is substrate, is prepared the branched TiO of the nanoparticle sensitized hydrogenation of CdS by the continuous chemical water-bath deposition repeatedly circulated 2nano-stick array membrane;
Single cycle is operating as the branched TiO of hydrogenation 2nano-stick array membrane is immersed in Cd (NO 3) 2in the aqueous solution, 3min afterflush is clean, then puts into Na 2the S aqueous solution, 3min afterflush is clean;
Repetitive cycling operates 3 times, obtains the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2nano-stick array membrane.
The branched TiO of the nanoparticle sensitized hydrogenation of the CdS prepared 2under the visible ray of nano-stick array membrane, photocatalytic hydrogen production by water decomposition speed is see Fig. 6.
Embodiment 4
(1) branched TiO 2the preparation of nano-stick array membrane
1. by ITO electro-conductive glass priority ultrasonic 30min in deionized water, acetone and ethanolic solution successively, clean through deionized water, dry up for subsequent use;
2. prepare the precursor solution in titanium source: first mixed with 20mL deionized water by 20mL concentrated hydrochloric acid (mass concentration is 37.5%), stir and add l mL butyl titanate and continue stirring 5 minutes afterwards for 5 minutes, obtain titanium source precursor solution;
3. the conducting surface of ITO electro-conductive glass is placed in reactor obliquely, adds titanium source precursor solution, react 8 hours under 150 DEG C of conditions, deionized water is washed, dry at 80 DEG C, obtains TiO 2nano-stick array membrane.
4. the TiO will prepared 2it is the TiCl of 0.01M that nanometer rods immerses containing 10mL concentration 3hydrochloric acid solution in, wherein content of hydrochloric acid is 0.01mL/10mL solution, and 80 DEG C of constant temperature growth 1h, obtain branched TiO 2nano-stick array membrane.
(2) by branched TiO 2nano-stick array membrane is placed in hydrogen atmosphere hydrogenation, and hydrogen atmosphere is the mist of hydrogen argon gas.The flow velocity of hydrogen is 20SCCM, and the flow velocity of argon gas is 80SCCM, and hydrogenation temperature is 350 DEG C, and hydrogenation time is 2h, obtains the branched TiO of hydrogenation 2nano-stick array membrane.
(3) the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2the preparation of nano-stick array membrane
1. Cd (the NO of 0.5M is prepared 3) 2the aqueous solution, the Na of 0.5M 2the S aqueous solution;
2. with the branched TiO of hydrogenation 2nano-stick array membrane is substrate, is prepared the branched TiO of the nanoparticle sensitized hydrogenation of CdS by the continuous chemical water-bath deposition repeatedly circulated 2nano-stick array membrane;
Single cycle is operating as the branched TiO of hydrogenation 2nano-stick array membrane is immersed in Cd (NO 3) 2in the aqueous solution, 3min afterflush is clean, then puts into Na 2the S aqueous solution, 3min afterflush is clean;
Repetitive cycling operates 7 times, obtains the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2nano-stick array membrane.
The branched TiO of the nanoparticle sensitized hydrogenation of the CdS prepared 2under the visible ray of nano-stick array membrane, photocatalytic hydrogen production by water decomposition speed is see Fig. 6.
Embodiment 5
(1) branched TiO 2the preparation of nano-stick array membrane
1. by ITO electro-conductive glass successively successively in deionized water, acetone and ethanolic solution ultrasonic 30 minutes, clean through deionized water, dry up for subsequent use;
2. prepare the precursor solution in titanium source: first mixed with 50mL deionized water by 50mL concentrated hydrochloric acid (mass concentration is 37.5%), stir and add l mL butyl titanate and continue stirring 5 minutes afterwards for 5 minutes, obtain titanium source precursor solution;
3. the conducting surface of ITO electro-conductive glass is placed in reactor obliquely, adds titanium source precursor solution, react 4 hours under 150 DEG C of conditions, deionized water is washed, dry at 80 DEG C, obtains TiO 2nano-stick array membrane.
4. the TiO will prepared 2it is the TiCl of 0.01M that nanometer rods immerses containing 10mL concentration 3in hydrochloric acid solution, wherein content of hydrochloric acid is 0.01mL/10mL solution, and 80 DEG C of constant temperature growth 1h, obtain branched TiO 2nano-stick array membrane.
(2) by branched TiO 2nano-stick array membrane is placed in hydrogen atmosphere hydrogenation, and hydrogen atmosphere is the mist of hydrogen argon gas.The flow velocity of hydrogen is 20SCCM, and the flow velocity of argon gas is 80SCCM, and hydrogenation temperature is 350 DEG C, and hydrogenation time is 2h, obtains the branched TiO of hydrogenation 2nano-stick array membrane.
(3) the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2the preparation of nano-stick array membrane
1. Cd (the NO of 0.5M is prepared 3) 2the aqueous solution, the Na of 0.5M 2the S aqueous solution;
2. with the branched TiO of hydrogenation 2nano-stick array membrane is substrate, is prepared the branched TiO of the nanoparticle sensitized hydrogenation of CdS by the continuous chemical water-bath deposition repeatedly circulated 2nano-stick array membrane;
Single cycle is operating as the branched TiO of hydrogenation 2nano-stick array membrane is immersed in Cd (NO 3) 2in the aqueous solution, 3min afterflush is clean, then puts into Na 2the S aqueous solution, 3min afterflush is clean;
Repetitive cycling operates 7 times, obtains the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2nano-stick array membrane.
The branched TiO of the nanoparticle sensitized hydrogenation of the CdS prepared 2under the visible ray of nano-stick array membrane, photocatalytic hydrogen production by water decomposition speed is see Fig. 6.
Embodiment 6
(1) branched TiO 2the preparation of nano-stick array membrane is with embodiment 1.
(2) by branched TiO 2nano-stick array membrane is placed in hydrogen atmosphere hydrogenation, and hydrogen atmosphere is the mist of hydrogen argon gas.The flow velocity of hydrogen is 20SCCM, and the flow velocity of argon gas is 80SCCM, and hydrogenation temperature is 400 DEG C, and hydrogenation time is 1h, obtains the branched TiO of hydrogenation 2nano-stick array membrane.
(3) the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2the preparation of nano-stick array membrane is with embodiment 1.
The branched TiO of the nanoparticle sensitized hydrogenation of the CdS prepared 2under the visible ray of nano-stick array membrane, photocatalytic hydrogen production by water decomposition speed is see Fig. 6.
Embodiment 7
(1) branched TiO 2the preparation of nano-stick array membrane is with embodiment 1.
(2) by branched TiO 2nano-stick array membrane is placed in hydrogen atmosphere hydrogenation, and hydrogen atmosphere is the mist of hydrogen argon gas.The flow velocity of hydrogen is 20SCCM, and the flow velocity of argon gas is 80SCCM, and hydrogenation temperature is 300 DEG C, and hydrogenation time is 3h, obtains the branched TiO of hydrogenation 2nano-stick array membrane.
(3) the branched TiO of the nanoparticle sensitized hydrogenation of CdS 2the preparation of nano-stick array membrane is with embodiment 1.
The branched TiO of the nanoparticle sensitized hydrogenation of the CdS prepared 2under the visible ray of nano-stick array membrane, photocatalytic hydrogen production by water decomposition speed is see Fig. 6.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a branched titanic oxide nanorod array film for sensitized by cadmium sulfide nanoparticles hydrogenation, is characterized in that the method by comprising the following steps prepares:
Using electro-conductive glass as substrate, be immersed in the heated in water solution reaction of butyl titanate and hydrochloric acid, then immerse TiCl 3hydrochloric acid solution in, obtain branched titanic oxide nanorod array film; Be placed on hydrogenation under atmosphere of hydrogen; Adopt cadmium sulfide nanoparticles in chemical deposition load again, obtain the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation.
2. the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1, is characterized in that: described electro-conductive glass refers to FTO electro-conductive glass, ITO electro-conductive glass, metallized glass or metal-oxide film glass.
3. the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1, is characterized in that: described butyl titanate and salt aqueous acid take volume ratio as the butyl titanate of 1:50:50 ~ 1:20:20, concentrated hydrochloric acid and water configuration obtain.
4. the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1, is characterized in that: described in add thermal response condition be 140 ~ 180 DEG C of reaction 4 ~ 8h; Described immersion TiCl 3hydrochloric acid solution in condition be 70 ~ 90 DEG C soak 0.5 ~ 2h; Described TiCl 3hydrochloric acid solution in TiCl 3concentration be 0.005 ~ 0.2M.
5. the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1, is characterized in that: the condition of described hydrogenation is 250 ~ 450 DEG C of hydrogenation 1 ~ 3h.
6. the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1, it is characterized in that: cadmium sulfide nanoparticles in the load of described employing chemical deposition, by the sulphur source precursor solution of first configuration concentration to be the cadmium source precursor solution of 0.05 ~ 1M and concentration be 0.05 ~ 1M, obtained the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation by the continuous chemical water-bath sedimentation of 3 ~ 15 sensitizations circulation.
7. the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1, is characterized in that: described cadmium source precursor solution is Cd (NO 3) 2the aqueous solution, CdCl 2the aqueous solution or CdSO 4the aqueous solution; Described sulphur source precursor solution is Na 2the S aqueous solution, K 2the S aqueous solution or (NH 4) 2the S aqueous solution.
8. based on a photocatalyst for the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1, it is characterized in that: obtain by the branched titanic oxide nanorod array film of sensitized by cadmium sulfide nanoparticles hydrogenation according to claim 1 is connected with wire.
9. the branched titanic oxide nanorod array film of the sensitized by cadmium sulfide nanoparticles hydrogenation according to any one of claim 1 ~ 7 decomposes the application in aquatic products hydrogen at visible light catalytic.
10. photocatalyst according to claim 8 decomposes the application in aquatic products hydrogen at visible light catalytic.
CN201510206125.4A 2015-04-27 2015-04-27 Cadmium sulfide sensitization hydrogenation branched titanium dioxide nanorod array membrane and light catalyst Pending CN104857942A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105347694A (en) * 2015-10-26 2016-02-24 华南理工大学 Branched heterogeneous hydrogenated titanium dioxide nanorod array electrode and preparation method thereof
CN109516495A (en) * 2018-12-13 2019-03-26 广东工业大学 A kind of load of tin oxide photonic crystal tungsten oxide and CdS semiconduct film and its preparation method and application
CN109694128A (en) * 2019-01-14 2019-04-30 南京工业大学 A kind of processing method of high concentration p-nitrophenol
CN114011372A (en) * 2021-11-30 2022-02-08 齐鲁工业大学 Bifunctional microstructure palladium-based membrane reactor and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2991195B1 (en) * 1998-08-19 1999-12-20 日本電気株式会社 Air purifier and air cleaning system using environmental catalyst
CN101969109A (en) * 2010-08-03 2011-02-09 襄樊学院 Preparation process of dendritic titanium dioxide nanotube array electrode
CN103151175A (en) * 2013-02-06 2013-06-12 天津大学 Cadmium sulfide (CdS) quantum dot sensitized branching titanium dioxide (TiO2) nanorod array electrode and preparation method and usage thereof
CN103523827A (en) * 2013-09-29 2014-01-22 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of three-dimensional dendritic TiO2 (titanium dioxide) array with rapid electronic transmission performance
CN104316581A (en) * 2014-10-23 2015-01-28 华南理工大学 Visible light photoelectrocatalysis based COD (chemical oxygen demand) sensor and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2991195B1 (en) * 1998-08-19 1999-12-20 日本電気株式会社 Air purifier and air cleaning system using environmental catalyst
CN101969109A (en) * 2010-08-03 2011-02-09 襄樊学院 Preparation process of dendritic titanium dioxide nanotube array electrode
CN103151175A (en) * 2013-02-06 2013-06-12 天津大学 Cadmium sulfide (CdS) quantum dot sensitized branching titanium dioxide (TiO2) nanorod array electrode and preparation method and usage thereof
CN103523827A (en) * 2013-09-29 2014-01-22 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of three-dimensional dendritic TiO2 (titanium dioxide) array with rapid electronic transmission performance
CN104316581A (en) * 2014-10-23 2015-01-28 华南理工大学 Visible light photoelectrocatalysis based COD (chemical oxygen demand) sensor and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105347694A (en) * 2015-10-26 2016-02-24 华南理工大学 Branched heterogeneous hydrogenated titanium dioxide nanorod array electrode and preparation method thereof
CN109516495A (en) * 2018-12-13 2019-03-26 广东工业大学 A kind of load of tin oxide photonic crystal tungsten oxide and CdS semiconduct film and its preparation method and application
CN109694128A (en) * 2019-01-14 2019-04-30 南京工业大学 A kind of processing method of high concentration p-nitrophenol
CN109694128B (en) * 2019-01-14 2021-12-28 南京工业大学 Method for treating high-concentration p-nitrophenol
CN114011372A (en) * 2021-11-30 2022-02-08 齐鲁工业大学 Bifunctional microstructure palladium-based membrane reactor and preparation method thereof
CN114011372B (en) * 2021-11-30 2023-03-17 齐鲁工业大学 Difunctional microstructure palladium-based membrane reactor and preparation method thereof

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