CN101623644B - Preparation for compound hollow sphere CdS-TiO* and application in photocatalytic hydrogen production by water decomposition - Google Patents

Preparation for compound hollow sphere CdS-TiO* and application in photocatalytic hydrogen production by water decomposition Download PDF

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CN101623644B
CN101623644B CN2009100235449A CN200910023544A CN101623644B CN 101623644 B CN101623644 B CN 101623644B CN 2009100235449 A CN2009100235449 A CN 2009100235449A CN 200910023544 A CN200910023544 A CN 200910023544A CN 101623644 B CN101623644 B CN 101623644B
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tio
nano
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hollow ball
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CN101623644A (en
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张耀君
闵超
李学进
王亚超
李圣
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Xian University of Architecture and Technology
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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
    • 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 preparation for compound hollow sphere CdS-TiO* and application in photocatalytic hydrogen production by water decomposition. The preparation method uses inexpensive cadmium source and titanium source, adopts a hydrothermal method, a two-step impregnation method and a sol-gel method for preparing compound hollow sphere CdS-TiO* nanophase materials; and the technical process is simple and practicable and can realize scale production. CdS and TiO2 are compounded, which broadens the spectral response range of TiO2; the prepared compound hollow sphere CdS-TiO is used as photocatalyst for solar energy visible light catalyzing hydrogen production by water decomposition; compared with the TiO2 photocatalyst, the optical energy utilization ratio of the solar energy is substantially increased and the speed of hydrogen production is obviously increased.

Description

Composite hollow ball CdS-TiO 2Preparation and application in photocatalytic hydrogen production by water decomposition
Technical field
The invention belongs to the preparation of nano composite material and in the application of new energy field.Be specifically related to a kind of composite hollow ball CdS-TiO 2Preparation of nanomaterials and this material thereof are as the application of photochemical catalyst in the solar visible light hydrogen production by water decomposition.
Background technology
Because the long-term uncontrolled exploitation of fossil energy, energy shortage has in recent years caused the great attention of various countries, thereby has accelerated the human paces of seeking new regenerative resource.Hydrogen Energy is with its clean burning, environmental protection, and is renewable pollution-free and become the focus that international community pays close attention to.Various countries are at all multipaths of trying to explore to obtain Hydrogen Energy, and utilizing the solar energy photocatalytic hydrogen production by water decomposition is recycling economy, one of effective way of green hydrogen manufacturing.
The key technology of utilizing the solar energy photocatalytic hydrogen production by water decomposition is a photochemical catalyst, TiO 2Be the Recent study photochemical catalyst of solar energy ultraviolet catalytic hydrogen production by water decomposition the most widely, yet, TiO 2The band gap of broad (Eg=3.2eV) makes its photocatalytic applications scope be subjected to certain restriction [1,2].In order to widen TiO 2Spectral response range, with its with have ideal bandgap (CdS, Eg=2.3eV), H compared on the conduction band limit +/ H 2The CdS coupling that electrode potential is more negative is one of effective way that improves solar energy utilization ratio.About CdS nano particle and TiO 2Nano particle (or nanotube) is compound and be used for the solar energy photocatalytic hydrogen production by water decomposition many reports [3-5] are arranged.And direct hollow ball CdS-TiO 2The preparation of nano composite material has only one piece of reported in literature, and people such as Hu [6] adopt a kind of method of solution reaction to prepare CdS-TiO 2Hollow ball, concrete grammar: Cadmium diacetate dihydrate and thiocarbamide, thioglycerol are dissolved in N, in the mixed solution of dinethylformamide and water, form solution 1, then with Ti (OBu) 4Be dissolved in formation solution 2 in the butanols with acetylacetone,2,4-pentanedione, solution 1 and solution 2 are mixed stirring, reflux, post processing obtains TiO 2/ CdS hollow ball composite construction.Look into newly through system, retrieve the patent [7-52] of more relevant preparation nano-hollow ball domestic and international patent, and direct nano-tube/CdS-TiO 2The patent of hollow ball preparation has only one [53]. and the present invention adopts the compound CdS-TiO of template-infusion process-Prepared by Sol Gel Method 2Hollow ball, and that document [6] and patent [53] report is the preparation method who adopts two kinds of solution reactions, so the present invention is with regard to nano-tube/CdS-TiO 2The preparation method of hollow ball is different fully with the method for document [6] and patent [53] report; With this nano-tube/CdS-TiO 2Hollow ball is used for the solar energy photocatalytic hydrogen production by water decomposition and does not see document and patent report.
Below be the list of references that the inventor provides:
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Figure G2009100235449D00051
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Summary of the invention
For the productive rate that the utilization ratio that improves solar energy and photochemical catalyzing prepare hydrogen, one of purpose of the present invention is that a kind of composite hollow ball CdS-TiO is provided 2Preparation of nanomaterials, this method adopts template-infusion process-Prepared by Sol Gel Method composite hollow ball CdS-TiO 2Nano material.Another object of the present invention is, with the composite hollow ball CdS-TiO of preparation 2Nano material is used for the exploratory application study of the new energy field of solar visible light catalytic decomposition water hydrogen manufacturing as photochemical catalyst.
In order to realize above-mentioned task, the CdS-TiO of composite hollow ball of the present invention 2The preparation method take following technical solution:
A kind of composite hollow ball CdS-TiO 2The preparation method, it is characterized in that this method adopts hydro-thermal method successively, two the step infusion processes, Prepared by Sol Gel Method composite hollow ball CdS-TiO 2, specifically comprise the following steps:
1) take by weighing an amount of sucrose and be mixed with aqueous sucrose solution, put into autoclave, hydro-thermal synthesis of nano carbon ball under suitable temperature is as hard mould agent;
2) take by weighing The addition of C d (NO 3) 24H 2O is mixed with the aqueous solution;
3) take by weighing an amount of Na 2S9H 2O is mixed with the aqueous solution;
4) at room temperature, the Nano carbon balls of step 1) is dispersed in the absolute ethyl alcohol, carries out ultrasonic wave and disperse, oven dry; With step 2) in Cd (NO 3) 24H 2The aqueous solution of O impregnated in the prepared Nano carbon balls of step 1), and room temperature is dried, and makes the Nano carbon balls C-Cd of cadmium ion parcel 2+, wherein, Nano carbon balls consumption 5mol, Cd (NO 3) 24H 2The consumption of O is between 0.079mol～0.14mol;
5) at room temperature, with the Na in the step 3) 2S9H 2The O aqueous solution slowly drops to the prepared Nano carbon balls C-Cd of step 4) 2+In, described Na 2S9H 2The O consumption is between 0.0936mol～0.168mol, and dipping spends the night, and oven dry obtains the Nano carbon balls C-CdS that cadmium sulfide wraps up;
6) take by weighing an amount of TiCl 4Be mixed with ethanolic solution;
7) the Nano carbon balls C-CdS that step 5) is made puts into the there-necked flask that has stirring, again with the TiCl of step 6) 4Ethanolic solution adds, and stirs described TiCl 4Consumption 0.06mol;
8) under constantly stirring, an amount of ammonia spirit is slowly splashed in the there-necked flask solution of step 7), regulating the pH value is 7-8, filters, and washing promptly makes on the carbon nuclear and is enclosed with cadmium sulfide and TiO successively 2Nucleocapsid structure C-CdS-TiO 2Composite;
9) nucleocapsid structure C-CdS-TiO that step 8) is prepared 2Composite in 400 ℃ of roasting 2h, obtains composite hollow ball CdS-TiO in Muffle furnace 2Nano material.
The composite hollow ball CdS-TiO of the present invention's preparation 2Nano material is used for the application study of solar visible light catalytic decomposition water hydrogen manufacturing as photochemical catalyst.As the analog solar light source, adopt optical filter to filter ultraviolet light with xenon lamp, estimate solar visible light catalytic decomposition water hydrogen manufacturing productive rate.Specifically comprise the following steps:
1) quantitatively takes by weighing hole sacrifice agent Na respectively 2S and Na 2SO 3Dissolve in the Prex glass flat-bottomed flask that 100mL illumination one side that fills 50mL distilled water is the plane, take by weighing an amount of composite hollow ball CdS-TiO 2Nano-powder is added in the reaction bulb;
2) reaction bulb is placed on the magnetic stirring apparatus, threeway sample introduction glass bottle stopper is inserted in the reaction bulb, open the xenon lamp stabilized current supply, with the ultraviolet light of optical filter elimination λ＜420nm, light source exposes to the reaction bulb side after seeing through optical filter;
3) the TCD detector that adopts gas chromatograph to be equipped with, the TDX-01 packed column detects the gas-phase product that generates, and estimates solar visible light catalytic decomposition water hydrogen manufacturing productive rate.
The composite hollow ball CdS-TiO of the present invention's preparation 2The technique effect that nano material and the application in the solar energy photocatalytic hydrogen production by water decomposition thereof bring is:
(1) can utilize cheap cadmium source and titanium source to prepare composite hollow ball CdS-TiO 2Nano material, technical process is simple, can realize scale preparation.
(2) composite hollow ball CdS-TiO 2Be the novel photocatalysis agent of function admirable, CdS and TiO 2Compound, widened TiO 2The spectrum respective range increases substantially solar energy luminous energy utilization ratio, and hydrogen generation efficiency obviously improves.
Innovation part of the present invention is:
(1) proposed to utilize cheap cadmium source and titanium source to prepare composite hollow ball CdS-TiO 2The new method of nano material.
(2) proposed composite hollow ball CdS-TiO 2Be used for the solar energy photocatalytic hydrogen production by water decomposition as photochemical catalyst, improved hydrogen-producing speed.
(3) CdS is coated on TiO 2Among, and adopt Na 2S-Na 2SO 3The sacrifice agent system has been avoided the generation of CdS photoetch phenomenon, has improved composite hollow ball CdS-TiO 2The life-span of photochemical catalyst and activity.
Description of drawings
Fig. 1. the block diagram of preparation C-CdS;
Fig. 2. preparation composite hollow ball CdS-TiO 2Block diagram;
Fig. 3. nucleocapsid structure C-CdS-TiO 2The SEM photo of composite;
Fig. 4. composite hollow ball CdS-TiO 2Nano material SEM photo;
Fig. 5. composite hollow ball CdS-TiO 2The TEM photo of nano material;
The present invention is described in further detail below in conjunction with embodiment that accompanying drawing and inventor provide.
The specific embodiment
Composite hollow ball CdS-TiO of the present invention 2Preparation of nanomaterials adopts the synthetic nano carbon microsphere of hydro-thermal method as hard template method, adopts two step infusion processes successively, and technology paths such as sol-gal process and roasting are prepared composite hollow ball CdS-TiO 2Nano material.In building-up process, the nano carbon microsphere consumption is 5mol; Cd (NO 3) 24H 2The O consumption is between 0.079mol～0.14mol; Na 2S9H 2The O consumption is between 0.0936mol～0.168mol; TiCl 4Consumption is 0.06mol.
The technology path of preparation C-CdS prepares composite hollow ball CdS-TiO as shown in Figure 1 2The nano material technology route as shown in Figure 2.
Below be the embodiment that the inventor provides, need to prove that these embodiment only in order better to annotate the present invention, the invention is not restricted to these embodiment.The chemical reagent that relates among the embodiment is AR.
Embodiment 1:
Take by weighing the glucose solids powder of 15g, measure the 150mL deionized water, the glucose solids powder is dissolved in the deionized water, evenly stir 10min.
The homogeneous solution that forms is poured in the teflon-lined autoclave (volume is 200mL), put into electrocaloric effect and be heated to 165 ℃, insulation reaction 5h takes out and naturally cools to room temperature.Filter, use deionized water and absolute ethanol washing three times respectively, solid is put into drying box dry 5h under 60 ℃ of conditions, makes brown Nano carbon balls.
Taking by weighing the brown Nano carbon balls 60g (5mol) of preparation, put into the beaker of absolute ethyl alcohol, is ultrasonic echography 30min under the 31Hz condition in frequency, 50 ℃ of oven dry.Take by weighing 42g (0.14mol) Cd (NO 3) 24H 2The O solid joins in the 80mL deionized water, is mixed with the aqueous solution.This solution impregnation in the 60g Nano carbon balls, is flooded 2h, and room temperature is dried, and makes the compound (C-Cd of Nano carbon balls parcel cadmium ion 2+).
Take by weighing the Na of 40.32g (0.168mol) 2S9H 2The O solid joins in the 80mL deionized water, is mixed with the aqueous solution.Draw this solution with dropper and slowly drop to the compound (C-Cd that the carbon bag is wrapped up in cadmium ion 2+) sample surfaces (should avoid the light source direct projection in the dropping process), dipping 2h filters, and 60 ℃ of freeze-day with constant temperature of drying box are put in washing, make the cadmium sulfide composite material sample (C-CdS) that the carbon bag is wrapped up in.
Measure 6.6mL (0.06mol) TiCl with dry graduated cylinder 4, slowly splash in the beaker that fills the 100mL absolute ethyl alcohol preparation titanium colloidal sol with dropper;
Put into the there-necked flask that fills the 150mL absolute ethyl alcohol with making the cadmium sulfide composite material sample (C-CdS) that the carbon bag wraps up in; Under stirring fast, the titanium colloidal sol of making is added in the there-necked flask.
Under constantly stirring, with ammonia spirit (NH 3H 2O: H 2O=1: 5) slowly splash in the there-necked flask, the p H value of regulator solution is 7-8, and a large amount of TiO are arranged 2Gel occurs, room temperature reaction 2h; Then after filtration, washing can make C (nuclear) parcel CdS (inferior shell) and wrap up TiO again 2The C-CdS-TiO of the nucleocapsid structure of (shell) 2Composite, SEM (SEM) photo as shown in Figure 3.
With prepared nucleocapsid structure C-CdS-TiO 2Composite, in Muffle furnace, roasting 2h under 400 ℃ of conditions makes TiO 2The composite hollow ball CdS-TiO of parcel CdS 2Nano material.Composite hollow ball CdS-TiO 2The SEM of nano material (SEM) photo as shown in Figure 4; Transmission electron microscope (TEM) photo as shown in Figure 5.
Embodiment 2:
Take by weighing the Na of sacrifice agent 1.25g respectively 2The Na of S and 0.25g 2SO 3Dissolve in the Prex glass flat-bottomed flask that 100mL illumination one side that fills 50mL distilled water is the plane.Take by weighing the composite hollow ball CdS-TiO of embodiment 1 preparation 2Nano-powder 0.10g adds in the reaction bulb.
Reaction bulb is placed on the magnetic stirring apparatus stirs, threeway sample introduction glass bottle stopper is inserted in the reaction bulb, with xenon lamp as the simulated solar light source, open the xenon lamp stabilized current supply, the ultraviolet light of optical filter elimination λ＜420nm, light source exposes to the reaction bulb side after optical filter filters, detect the composite hollow ball CdS-TiO of radiation of visible light 6h 2The photocatalytic hydrogen production by water decomposition activity of catalyst.The TCD detector of gas chromatograph assembling, TDX-01 packed column are adopted in the detection of hydrogen.Solar visible light catalytic decomposition aquatic products H 2The result is as shown in table 1.
Table 1: composite hollow ball CdS-TiO 2Solar visible light catalytic decomposition aquatic products H 2The result
Light application time (h) 1 2 3 4 5 6
?H 2(mL/g) 0.81 2.10 3.81 5.56 7.43 9.16
Embodiment 3:
Whole implementation step is same as embodiment 1, and different is: (1) takes by weighing 24g (0.78mol) Cd (NO 3) 24H 2The O solid joins in the 80mL deionized water, is mixed with the aqueous solution; (2) take by weighing 22.46g (0.0936mol) Na 2S9H 2The O solid in the deionized water, is mixed with the aqueous solution.
Embodiment 4:
Whole implementation step is same as embodiment 2, and that different is the composite hollow ball CdS-TiO that takes by weighing embodiment 3 preparations 2Nano-powder 0.10g puts into reaction bulb.Solar visible light catalytic decomposition aquatic products H 2The result is as shown in table 2.
Table 2. composite hollow ball CdS-TiO 2Solar visible light catalytic decomposition aquatic products H 2The result
Light application time (h) 1 2 3 4 5 6
?H 2(mL/g) 0.46 1.27 2.16 3.24 3.87 4.82

Claims (4)

1. composite hollow ball CdS-TiO 2The preparation method, it is characterized in that this method adopts hydro-thermal method successively, two the step infusion processes, Prepared by Sol Gel Method composite hollow ball CdS-TiO 2, specifically comprise the following steps:
1) take by weighing an amount of sucrose and be mixed with aqueous sucrose solution, put into autoclave, hydro-thermal synthesize nano carbon ball under suitable temperature is as hard mould agent;
2) take by weighing The addition of C d (NO 3) 24H 2O is mixed with the aqueous solution;
3) take by weighing an amount of Na 2S9H 2O is mixed with the aqueous solution;
4) at room temperature, the Nano carbon balls of step 1) is dispersed in the absolute ethyl alcohol, carries out ultrasonic wave and disperse, oven dry; The Nano carbon balls that step 1) is prepared impregnated in step 2) in Cd (NO 3) 24H 2In the aqueous solution of O, room temperature is dried, and makes the Nano carbon balls C-Cd of cadmium ion parcel 2+, wherein, Nano carbon balls consumption 5mol, Cd (NO 3) 24H 2The consumption of O is between 0.079mol～0.14mol;
5) at room temperature, with the Na in the step 3) 2S9H 2The O aqueous solution slowly drops to the prepared Nano carbon balls C-Cd of step 4) 2+In, described Na 2S9H 2The O consumption is between 0.0936mol～0.168mol, and dipping washs, and oven dry obtains the Nano carbon balls C-CdS that cadmium sulfide wraps up;
6) take by weighing an amount of TiCl 4Be mixed with ethanolic solution;
7) the Nano carbon balls C-CdS that step 5) is made puts into the there-necked flask that has stirring, again with the TiCl of step 6) 4Ethanolic solution adds, and stirs described TiCl 4Consumption 0.06mol;
8) under constantly stirring, an amount of ammonia spirit is slowly splashed in the there-necked flask solution of step 7), regulating the pH value is 7-8, filters, and washing promptly makes on the carbon nuclear and is enclosed with cadmium sulfide and TiO successively 2Nucleocapsid structure C-CdS-TiO 2Composite;
9) nucleocapsid structure C-CdS-TiO that step 8) is prepared 2Composite in 400 ℃ of roasting 2h, obtains composite hollow ball CdS-TiO in Muffle furnace 2Nano material.
2. the composite hollow ball CdS-TiO of the described method of claim 1 preparation 2Nano material is used for the application of solar visible light catalytic decomposition water hydrogen manufacturing as photochemical catalyst.
3. the described application of claim 2 is characterized in that, adopts xenon lamp as the analog solar light source, adopts optical filter to filter ultraviolet light, estimates solar visible light catalytic decomposition water hydrogen manufacturing productive rate.
4. the described application of claim 2 is characterized in that, comprises the following steps:
1) quantitatively takes by weighing hole sacrifice agent Na respectively 2S and Na 2SO 3Dissolve in the Prex glass flat-bottomed flask that 100mL illumination one side that fills 50mL distilled water is the plane, take by weighing an amount of composite hollow ball CdS-TiO 2Nano-powder is added in the reaction bulb;
2) reaction bulb is placed on the magnetic stirring apparatus, threeway sample introduction glass bottle stopper is inserted in the reaction bulb, open the xenon lamp stabilized current supply, with the ultraviolet light of optical filter elimination λ＜420nm, light source exposes to the reaction bulb side after seeing through optical filter;
3) the TCD detector that adopts gas chromatograph to be equipped with, the TDX-01 packed column detects the gas-phase product that generates, and estimates solar visible light catalytic decomposition water hydrogen manufacturing productive rate.
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