CN101623645A - Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition - Google Patents
Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition Download PDFInfo
- Publication number
- CN101623645A CN101623645A CN200910023546A CN200910023546A CN101623645A CN 101623645 A CN101623645 A CN 101623645A CN 200910023546 A CN200910023546 A CN 200910023546A CN 200910023546 A CN200910023546 A CN 200910023546A CN 101623645 A CN101623645 A CN 101623645A
- Authority
- CN
- China
- Prior art keywords
- cds
- nano
- nio
- weighing
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses preparation for p-n junction hollow sphere TiO-CdS nanophase compound material and application in photocatalytic hydrogen production by water decomposition; the method uses inexpensive cadmium source and nickel source, adopts a hydrothermal method, a synthesis method, and a four-step impregnation method for compounding an n-NiO semiconductor and a p-CdS semidconductor to prepare the p-n junction hollow sphere TiO-CdS nanophase compound material; and the technical process is simple and practicable and can realize scale production. The p-n junction hollow sphere TiO-CdS nanophase compound material is used as photocatalyst for solar energy visible light catalyzing hydrogen production by water decomposition, speeds up the conveying rate of photo-generated electrons and substantially increases yield of the hydrogen production.
Description
Technical field
The invention belongs to the preparation of nano composite material and the application in new energy field thereof.The p-n junction hollow ball NiO-CdS nano composite material that is specifically related to a kind of preparation method of p-n junction hollow ball NiO-CdS nano composite material and preparation thereof as photocatalyst applications in the hydrogen manufacturing of solar visible light catalytic decomposition water.
Background technology
In recent years, because the greenhouse effects that energy shortage and use fossil energy cause have brought new challenge for the sustainable development of global economy.Therefore, strengthen the energy science and technology innovation, tap a new source of energy, not only the human current living environment of influence more concerns the future development in the mankind.Exploitation clean energy resource, raising energy efficiency promote energy savings, reduce discharging, are just becoming the common objective of various countries.Solar energy is the human inexhaustible permanent energy, and 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.Solar energy is converted into Hydrogen Energy to greatest extent all multipaths, 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 photochemical catalyst [1,2].CdS is with its narrow band gap (Eg=2.3eV), and desirable visible absorption bands of a spectrum are the indispensable photochemical catalysts of solar visible light catalytic decomposition water hydrogen manufacturing.But owing to the photoetch of CdS has limited its development, people utilize several different methods that it is modified, to improve its photostability [3-8].To make p-n junction hollow ball NiO-CdS nano composite material among the NiO be to improve a kind of new trial of CdS photostability and CdS is coated on.Look into newly through system domestic and international patent, retrieve the patent report [9-55] of more relevant nano-hollow ball preparation, and the directly preparation of p-n junction hollow ball NiO-CdS nano composite material and this composite hollow ball is used for the solar energy photocatalytic hydrogen production by water decomposition does not see document and patent report.
Below be the list of references that the inventor provides:
[1]M?Matsuoka，M.Kitano，M.Takeuchi，K.Tsujimaru，M.Anpo，J.M.Thomas，Photocatalysis?for?new?energy?production?recentadvances?in?photocatalytic?water?splitting?reactions?forhydrogen?production，Catalysis?Today?122(2007)51-61。
[2]J.R.Bolton，Solar?photoproduction?of?hydrogen：a?review，SolarEnergy?57(1996)37-50。
[3]Buhler?N，Meier?K，Reber?J.Photochemical?hydrogen?production?withcadmium?sulfide?suspensions.J?Phy?Chem?1984；88：3261-8。
[4]Fox?MA，Pettit?TL.Photoactivity?of?zeolite-supported?cadmiumsulfide：hydrogen?evolution?in?the?presence?of?sacrificialdonors.Langmuir?1989；5：1056-61。
[5]Hirai?T，Nanba?M，Komasawa?I.Dithiol-mediated?incorporation?ofCdS?nanoparticles?from?reverse?micellar?system?into?Zn-dopedSBA-15?mesoporous?silica?and?their?photocatalytic?properties.J?Colloid?Interface?Sci?2003；268：394-9。
[6]Hirai?T，Bando?Y.Immobilization?of?CdS?nanoparticles?formedin?reverse?micelles?onto?aluminosil?icate?supports?and?theirphotocatalytic?properties.J?Colloid?Interface?Sci2005；288(2)：513-6。
[7]Guan?G，Kida?T，Kusakabe?K，Kimura?K，Fang?X，Ma?T，Abe?E，YoshidaA.Photocatalytic?H
2?evolution?under?visible?light?irradiation?onCdS/ETS-4?composite.Chem?Phy?Lett?2004；385：319-22。
[8]Guan?G，Kida?T，Kusakabe?K，Kimura?K，Abe?E，Yoshida?A.Photocatalyticactivity?of?CdS?nanoparticles?incorporated?in?titanium?silicatemolecular?sieves?of?ETS-4?and?ETS-10.Appl?Catal?A?Gen2005；295(1)：71-8。
[9]. Li Yadong, Peng Qing, Dong Yajie, a kind of synthetic method of micron order zinc selenide hollow ball, publication number: CN1424248.
[10]. Liao Chuanping, Gu Mingyuan, carbon hollow nanospheres and preparation method thereof, publication number: CN1438174.
[11]. Liu Huizhou, sheep is refined, Guo Chen, the synthetic method with hollow silica ball of mesopore orbit of dodecyl sodium sulfate regulation and control, publication number: CN101143724.
[12]. Guo Fen, Pang Liping, a kind of preparation method of nano alumina hollow ball, publication number: CN101134586.
[13]. Liu Xiaohe, Wu Hongyi, Qiu Guanzhou, the preparation method of electric polypyrrole nano hollow sphere, publication number: CN101165092.
[14]. Li Chunzhong, Liu Jie, Hu Yanjie, a kind of preparation method of hollow ball structure titanium dioxide, publication number: CN101215004.
[15]. Wang Xia, Yang Guangzhi, Yang Junhe, Chen Min, Xu Risheng is the method that presoma prepares carbon nano-hollow sphere with polymethyl methacrylate/polyacrylonitrile nucleocapsid polymer, publication number: CN101219785.
[16]. Xie Rongguo, Li Dongsheng, Yang Deren prepares the method for monodisperse CdS hollow ball, publication number: CN1559911.
[17]. bandit Hua Min, Wang Jing, Pan Yubai, Guo Jingkun, a kind of preparation method of the alumina hollow ball based on wet chemistry method, publication number: CN1673085.
[18]. Jia Dian gives, Cao Yali, Liu Lang, a kind of solid state reaction prepares the method for zinc oxalate nano-hollow ball and hollow chain, publication number: CN1493559.
[19]. bandit Hua Min, Wang Jing, Pan Yubai, Guo Jingkun is the preparation method of the Zinc oxide hollow spheres of raw material with the zinc powder, publication number: CN1706774.
[20]. Xia Xinghua, fourth Ya, the preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls, publication number: CN1721075.
[21]. Bao Jianchun, Zhang Jie, Dai Zhihui, the preparation method of nano-grade cadmium sufide hollow ball, publication number: CN1792811.
[22]. Qiu Jieshan, Sun Tianjun, Zhao Zongbin, the batch synthesis method of zinc-oxide nano/micrometre hollow sphere, publication number: CN1803624.
[23]. Yu Shuhong, ten thousand is brave, a kind of preparation method of hollow silica ball, publication number: CN1931718.
[24]. Yu Shuhong, Min Yulin, a kind of synthetic method that includes the hollow silica ball of noble metal nano particles, publication number: CN1943927.
[25]. Cao Yanxia, Wang Jingwu, Wang Wanjie, the preparation method of stannic oxide hollow sphere, publication number: CN101012067.
[26]. Zhu person of outstanding talent, Miu Jianjun, Jiang Liping, the preparation method of a kind of CdTe nano-hollow ball or CdTe nanotube, publication number: CN101049916.
[27]. Zhu Haitao, Wang Jixin, Zhang Canying, a kind of preparation method of copper sulfide hollow ball, publication number: CN101054197.
[28]. Li Cun, Wu Zhenyu, Xu Hongyao, a kind of liquid phase preparation process of Nano cadmium sulphide hollow ball, publication number: CN101058437.
[29]. high Lian, Chen Zhitao a kind ofly prepares the method for zinc oxide nano hollow spheres, publication number: CN101254939 by caustic corrosion reaction.
[30]. Sun Yuhan, high love, Xu Yao, a kind of preparation method of double-channel mesoporous silicon oxide hollow sphere, publication number: CN101264892.
[31]. Lu Anhui, agricultural paddy treasure, Qian Huaguang, the method for synthetic hollow carbon case of a step, publication number: CN101314467.
[32]. wish Hua Yun, Zhang Xiaobin, Mi Yuhong, Zhou Shengming, Zhou Lina, ox is strong, Tan Junjun, Cui Baixue, Cheng Jipeng, Liu Fu, Xu Guoliang, a kind of method for preparing hollow spherical cadmium sulfide nanocrystalline, publication number: CN101319404.
[33]. Deng Yonghui, Liu Jia, Liu
, Zhao Dongyuan, a kind of magnetic inorganic hollow compound microsphere and preparation method thereof, publication number: CN101345112.
[34]. Cao Xia prepares the method for metal nickel nano hollow bal, publication number: CN101417341.
[35]. high Lian, Song Xuefeng need not the wet chemical preparation method of the nickel oxide hollow microsphere of template, publication number: CN101417823.
[36]. Wang Han, Wu Aijun, Geng Keming, Zhu Dexian, Zhang Tao wafts Tan Qinghua, Shi Pengkun, a kind of magnesian alumina hollow ball product, publication number: CN101429044 of containing recklessly.
[37].S.Roland，B.Alexander，S.Guenter，B.Frank，Publication?number：DE10160640(A1)。
[38].N.Takayuki，Expanded?hollow?micro?sphere?composite?beads?andmethod?for?their?production，Publication?number：US?6225361(B1)。
[39].K.Koji，M.Kuniteru，S.Yoshimasa，Producion?of?hollow?fine?metalsphere，Publication?number：JP2305970(A)。
[40]. Yu Shuhong, Min Yulin, a kind of preparation method who includes the titanium dioxide hollow ball of gold nano grain, publication number: CN101085465;
[41]. Zhu person of outstanding talent, Miu Jianjun, Jiang Liping, CdS, CdSe or CdTe hollow Nano ring and method for making thereof, publication number: CN101049958;
[42]. Wang Zhaoqun, Kong Xuanfeng, Li Yunxing, Wu Qian, the preparation method of nano-level crosslinked polystyrene hollow microsphere, publication number: CN101125903;
[43]. Song Limin, Zhang Shujuan, Chen Bin, the solvent process for thermosynthesizing of lead fluoride hollow nanospheres, publication number: CN101391805;
[44]. Wang Zhilin, Chen Zhiming, a kind of method for preparing composite rare-earth fluoride nano hollow sphere, publication number: CN101386422.
[45]. Yu Chengzhong, Tang Jiawei, Zhu Jie, Wang Yunhua, a kind of nano-silicon dioxide hollow sphere material and preparation method thereof, publication number: CN101343065.
[46]. lift a sail, Wu Qiang, Ma Yanwen levies a kind of original position template method for preparing the AlN nano-hollow ball, publication number: CN101279723 recklessly.
[47]. white jade person of outstanding talent, Pang Linlin, Zhu Huiling, QiYong Xin, Bi Jianqiang, a kind of current techique for preparing the nano hollow carbon ball, publication number: CN101264878.
[48]. Yang Zhenglong, Qin Shen, period-luminosity is refined, letter spit of fland, Pu, Yuan person of outstanding talent, hollow nano silica dioxide micro-sphere/polyurethane composite aqueous paint and preparation method thereof, publication number: CN101250374.
[49]. Li Hui, Xu Ye, Li Hexing, a kind of hollow amorphous alloy nano-sphere catalyst and its production and application, publication number: CN101380577.
[50]. Yang Deren, Du Ning, Zhang Hui, a kind of method for preparing metallic oxide hollow nano-sphere, publication number: CN101310851.
[51]. Wang Ming, Cao Xueli, Fang Ming, Zhang Lide, reticular nano hole zinc oxide micron hollow ball and preparation method thereof, publication number: CN101311119.
[52]. Li Chunzhong, Hu Yanjie, Gu Feng, Jiang Haibo, a kind of preparation method of nano alumina hollow ball structure, publication number: CN1884083.
[53]. high Lian, Chen Minghai a kind ofly prepares the method for silver-colored nano-hollow ball, publication number: CN1762622 by displacement reaction.
[54]. Liang Hanpu, Wan Lijun, Bai Chunli, the preparation method of a kind of nano metal and bimetallic hollow ball, publication number: CN1616165.
[55]. Hu sturdy pines, Wan Lijun, Bai Chunli, a kind of inorganic semiconductor composite Nano level hollow ball and preparation method, publication number: CN1600674.
Summary of the invention
In order to improve solar energy utilization ratio and visible light catalytic hydrogen production by water decomposition productive rate.An object of the present invention is to provide a kind of preparation method of p-n junction hollow ball NiO-CdS nano composite material, this method adopts template and four step immersion process for preparing p-n junction hollow ball NiO-CdS nano composite materials; Another object of the present invention is the exploratory application study that the p-n junction hollow ball NiO-CdS nano composite material of preparation is used for the hydrogen manufacturing of solar visible light catalytic decomposition water as photochemical catalyst.
In order to realize above-mentioned task, following technical solution is taked in the preparation of p-n junction hollow ball NiO-CdS nano composite material of the present invention:
A kind of p-n junction hollow ball NiO-CdS nano composite material preparation method is characterized in that, this method adopts hydro-thermal method and four step infusion processes and roasting to prepare p-n junction hollow ball NiO-CdS nano composite material, specifically comprises 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 the 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 microsphere of step 1), and room temperature is dried, and makes the nano carbon microsphere C-Cd of cadmium ion parcel
2+, wherein, the nano carbon microsphere consumption is 0.83mol, Cd (NO
3)
24H
2The O consumption is 0.023mol;
5) at room temperature, with the Na in the step 3)
2S9H
2The aqueous solution of O slowly drops to the prepared C-Cd of step 4)
2+In, dipping, washing, oven dry obtains the Nano carbon balls C-CdS that cadmium sulfide wraps up, wherein, described Na
2S9H
2O consumption 0.028mol;
6) take by weighing an amount of Ni (NO
3)
26H
2O is mixed with the aqueous solution;
7) Ni (NO that step 6) is made
3)
26H
2The O aqueous solution slowly drops among the prepared C-CdS of step 5), dipping, and room temperature is dried, and makes the cadmium sulfide Nano carbon balls C-CdS-Ni that nickel ion coats
2+Wherein, Ni (NO
3)
26H
2O consumption 0.012mol;
8) take by weighing an amount of NaOH and be mixed with the aqueous solution, slowly drop to the prepared cadmium sulfide Nano carbon balls C-CdS-Ni of step 7)
2+In, wherein, NaOH consumption 0.029mol, dipping spends the night, washing, oven dry promptly makes the composite C-CdS-NiOH that wraps up cadmium sulfide and NiOH nucleocapsid structure on the carbon nuclear successively;
9) composite material of core-shell structure C-CdS-NiOH that step 8) is prepared in 400 ℃ of roasting 2h, obtains p-n junction hollow ball NiO-CdS nano composite material in Muffle furnace.
The present invention as photochemical catalyst, can be used in solar visible light catalytic decomposition water hydrogen manufacturing research with the p-n junction hollow ball NiO-CdS nano composite material of preparation.Application process as the analog solar light source, adopts optical filter to filter ultraviolet light with xenon lamp, estimates solar visible light catalytic decomposition water hydrogen manufacturing productive rate, specifically comprises the following steps:
1) quantitatively takes by weighing 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.Taking by weighing a certain amount of p-n junction hollow ball NiO-CdS nano composite material powder adds in the mixed liquor.
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 gas-phase product to generating of TDX-01 packed column detects, and estimates solar visible light catalytic decomposition water hydrogen production activity.
The technique effect that the p-n junction hollow ball NiO-CdS nano composite material of the present invention's preparation and the application in the solar energy photocatalytic hydrogen production by water decomposition thereof bring is:
(1) can utilize cheap nickel source and cadmium source to prepare p-n junction hollow ball NiO-CdS composite, technical process is simple, can realize scale preparation.
(2) with the photochemical catalyst of this p-n junction hollow ball NiO-CdS composite as the hydrogen manufacturing of solar visible light catalytic decomposition water, after being subjected to solar visible light irradiation, the light induced electron that the n-CdS semiconductor produces is transferred to the p-NiO semiconductor surface fast by p-n junction, improve the efficiency of transmission of light induced electron, improved the hydrogen manufacturing productive rate.
Innovation part of the present invention is:
(1) proposes to utilize cheap nickel source and cadmium source, utilized the new method of the p-NiO semiconductor and the n-CdS interface coupling preparation p-n junction hollow ball NiO-CdS composite of generation in the reaction.
(2) proposed p-n junction hollow ball NiO-CdS composite is used for the hydrogen manufacturing of solar visible light catalytic decomposition water as photochemical catalyst, this hydrogen production process is pollution-free, environmental protection.
Description of drawings
Fig. 1. preparation p-n junction hollow ball NiO-CdS nano composite material technology path;
Fig. 2. the SEM photo of nucleocapsid structure C-CdS-NiOH composite;
Fig. 3 .p-n junction hollow sphere NiO-CdS nano composite material SEM photo;
Below be that the present invention is described in further detail for the embodiment that provides in conjunction with the accompanying drawings of inventor.
The specific embodiment
The preparation method of the p-n junction hollow ball NiO-CdS nano composite material of the present invention's preparation adopts the hydro-thermal method synthetic method, technology paths such as four step infusion processes and roasting.In the preparation method, the consumption of nano carbon microsphere is 0.83mol, Cd (NO
3)
24H
2The consumption of O is 0.023mol, Na
2S9H
2The consumption of O is 0.028mol, Ni (NO
3)
26H
2The consumption of O is 0.012mol, and the consumption of NaOH is 0.029mol.The technology path of preparation as shown in Figure 1.
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, glucose 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 baking oven and be heated to 165 ℃, and, take out and naturally cool to room temperature at 165 ℃ of following insulation reaction 5h.Filter, use deionized water and absolute ethanol washing three times respectively, solid is put into 60 ℃ of dry 5h of drying box, the brown nano carbon microsphere that makes.
Taking by weighing the nano carbon microsphere 10g (0.83mol) of preparation, put into beaker, is ultrasonic echography 30min under the 31Hz condition in frequency, 50 ℃ of oven dry; Take by weighing the Cd (NO of 7g (0.023mol)
3)
24H
2The O solid joins in the 20mL deionized water, is mixed with the aqueous solution.This solution impregnation in the Nano carbon balls of 10g, 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 6.72g (0.028mol) Na
2S9H
2The O solid joins in the 20mL deionized water, is mixed with the aqueous solution.Draw the compound (C-Cd that this solution slowly drops to Nano carbon balls parcel cadmium ion with dropper
2+) sample surfaces (should avoid the light source direct projection in the dropping process), dipping 2h filters, and 40 ℃ of freeze-day with constant temperature of drying box are put in washing, make cadmium sulfide (C-CdS) composite sample that the carbon bag is wrapped up in.
Take by weighing the Ni (NO of 4.65g (0.012mol)
3)
26H
2O dissolves in the 7mL deionized water, is mixed with the aqueous solution.This solution is slowly dropped in the C-CdS sample, dipping 2h, room temperature is dried, and makes the cadmium sulfide nano carbon ball (C-CdS-Ni that nickel ion coats
2+).
Take by weighing 1.16g (0.029mol) NaOH, dissolve in the 7mL deionized water, be mixed with the aqueous solution.This solution is slowly dropped to C-CdS-Ni
2+In the sample, dipping spends the night, filter, and washing, 50 ℃ of oven dry,, making the nucleocapsid structure C-CdS-NiOH composite that C (nuclear) parcel CdS (inferior shell) wraps up NiOH (shell) again, SEM (SEM) photo is as shown in Figure 2.
With prepared nucleocapsid structure C-CdS-NiOH composite, 400 ℃ of roasting 2h in Muffle furnace prepare a kind of p-n junction hollow ball NiO-CdS nano composite material.SEM (SEM) photo as shown in Figure 3.
Embodiment 2:
Take by weighing the Na of hole 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.The p-n junction hollow ball NiO-CdS nano composite material 0.10g that takes by weighing preparation among the embodiment 1 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, behind the detection radiation of visible light 6h, and p-n junction hollow ball NiO-CdS nano composite material photocatalytic hydrogen production by water decomposition activity.Gas chromatograph, TCD detector, TDX-01 packed column, solar visible light catalytic decomposition aquatic products H are adopted in the detection of hydrogen
2The result is as shown in table 1.
Table 1.p-n junction hollow sphere NiO-CdS solar visible light catalytic decomposition aquatic products H
2The result
Claims (4)
1, a kind of preparation method of p-n junction hollow ball NiO-CdS nano composite material is characterized in that, this method adopts hydro-thermal method synthetic method and four step immersion process for preparing p-n junction hollow ball NiO-CdS nano composite materials, specifically comprises 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 the 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 microsphere of step 1), and room temperature is dried, and makes the nano carbon microsphere C-Cd of cadmium ion parcel
2+, wherein, the nano carbon microsphere consumption is 0.83mol, Cd (NO
3)
24H
2The O consumption is 0.023mol;
5) at room temperature, with the Na in the step 3)
2S9H
2The aqueous solution of O slowly drops to the prepared C-Cd of step 4)
2+In, dipping, washing, oven dry obtains the Nano carbon balls C-CdS that cadmium sulfide wraps up, wherein, described Na
2S9H
2O consumption 0.028mol;
6) take by weighing an amount of Ni (NO
3)
26H
2O is mixed with the aqueous solution;
7) Ni (NO that step 6) is made
3)
26H
2The O aqueous solution slowly drops among the prepared C-CdS of step 5), dipping, and room temperature is dried, and makes the cadmium sulfide Nano carbon balls C-CdS-Ni that nickel ion coats
2+Wherein, Ni (NO
3)
26H
2O consumption 0.012mol;
8) take by weighing an amount of NaOH and be mixed with the aqueous solution, slowly drop to the cadmium sulfide Nano carbon balls C-CdS-Ni that the prepared nickel ion of step 7) coats
2+In, wherein, NaOH consumption 0.029mol, dipping spends the night, washing, oven dry promptly makes the composite C-CdS-NiOH that wraps up cadmium sulfide and NiOH nucleocapsid structure on the carbon nuclear successively;
9) composite material of core-shell structure C-CdS-NiOH that step 8) is prepared in 400 ℃ of roasting 2h, obtains p-n junction hollow ball NiO-CdS nano composite material in Muffle furnace.
2, the p-n junction hollow ball NiO-CdS nano composite material of claim 1 method preparation 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 elimination 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 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 p-n junction hollow ball NiO-CdS nano composite material powder and add in the mixed liquor;
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100235468A CN101623645B (en) | 2009-08-10 | 2009-08-10 | Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100235468A CN101623645B (en) | 2009-08-10 | 2009-08-10 | Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101623645A true CN101623645A (en) | 2010-01-13 |
| CN101623645B CN101623645B (en) | 2011-01-26 |
Family
ID=41519726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100235468A Expired - Fee Related CN101623645B (en) | 2009-08-10 | 2009-08-10 | Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101623645B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102188980A (en) * | 2011-04-01 | 2011-09-21 | 河北工业大学 | Ternary core-shell composite photocatalyst and preparation method thereof |
| CN102205224A (en) * | 2011-04-20 | 2011-10-05 | 浙江理工大学 | Method for preparing CdS/TiO2 nanocomposite |
| CN102205223A (en) * | 2011-04-21 | 2011-10-05 | 浙江理工大学 | Method for preparing TiO2/CdS nanocomposite |
| CN103316693A (en) * | 2013-07-03 | 2013-09-25 | 西北师范大学 | Photocatalyst Cd/CdS containing catalyst promoter Cd as well as preparation method and application of photocatalyst Cd/CdS in photocatalysis hydrogen production reaction |
| CN105239091A (en) * | 2014-07-10 | 2016-01-13 | 中国科学院理化技术研究所 | Photocathode based on metallic oxides, quantum dots and hydrogen generation catalyst and preparation method and application of photocathode |
| CN107200363A (en) * | 2017-05-22 | 2017-09-26 | 安徽建筑大学 | Core shell structure NiO CdS Coaxial Nanofibers and preparation method thereof |
| CN109701560A (en) * | 2019-02-25 | 2019-05-03 | 淮阴工学院 | Composite photo-catalyst and preparation method thereof |
| CN109786677A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of zinc-nickel single flow battery positive electrode and preparation and application |
| CN110237675A (en) * | 2019-07-17 | 2019-09-17 | 烟台大学 | A kind of preparation method and application of high activity fluorine fixing material |
| CN110508293A (en) * | 2019-09-05 | 2019-11-29 | 合肥学院 | A kind of hollow multistage p-n junction NiO@CdS composite nano materials and preparation method thereof for photolysis water hydrogen |
| CN115228874A (en) * | 2022-05-25 | 2022-10-25 | 海南省智慧环境投资控股有限公司 | Dynamic circulation organic solid waste treatment process |
| CN115739121A (en) * | 2022-11-14 | 2023-03-07 | 中国科学院福建物质结构研究所 | Metal-coated composite semiconductor material and preparation method and application thereof |
| CN116713009A (en) * | 2023-06-06 | 2023-09-08 | 常州大学 | Preparation method and application of ZnCdS/NiO composite photocatalyst |
-
2009
- 2009-08-10 CN CN2009100235468A patent/CN101623645B/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102188980A (en) * | 2011-04-01 | 2011-09-21 | 河北工业大学 | Ternary core-shell composite photocatalyst and preparation method thereof |
| CN102205224A (en) * | 2011-04-20 | 2011-10-05 | 浙江理工大学 | Method for preparing CdS/TiO2 nanocomposite |
| CN102205224B (en) * | 2011-04-20 | 2012-12-26 | 浙江理工大学 | Method for preparing CdS/TiO2 nanocomposite |
| CN102205223A (en) * | 2011-04-21 | 2011-10-05 | 浙江理工大学 | Method for preparing TiO2/CdS nanocomposite |
| CN102205223B (en) * | 2011-04-21 | 2012-12-26 | 浙江理工大学 | Method for preparing TiO2/CdS nanocomposite |
| CN103316693A (en) * | 2013-07-03 | 2013-09-25 | 西北师范大学 | Photocatalyst Cd/CdS containing catalyst promoter Cd as well as preparation method and application of photocatalyst Cd/CdS in photocatalysis hydrogen production reaction |
| CN105239091A (en) * | 2014-07-10 | 2016-01-13 | 中国科学院理化技术研究所 | Photocathode based on metallic oxides, quantum dots and hydrogen generation catalyst and preparation method and application of photocathode |
| CN107200363B (en) * | 2017-05-22 | 2018-08-21 | 安徽建筑大学 | Nucleocapsid NiO-CdS Coaxial Nanofibers and preparation method thereof |
| CN107200363A (en) * | 2017-05-22 | 2017-09-26 | 安徽建筑大学 | Core shell structure NiO CdS Coaxial Nanofibers and preparation method thereof |
| CN109786677A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of zinc-nickel single flow battery positive electrode and preparation and application |
| CN109786677B (en) * | 2017-11-10 | 2021-11-16 | 中国科学院大连化学物理研究所 | Positive electrode material for zinc-nickel single flow battery, preparation and application |
| CN109701560A (en) * | 2019-02-25 | 2019-05-03 | 淮阴工学院 | Composite photo-catalyst and preparation method thereof |
| CN109701560B (en) * | 2019-02-25 | 2021-09-24 | 淮阴工学院 | Composite photocatalyst and preparation method thereof |
| CN110237675A (en) * | 2019-07-17 | 2019-09-17 | 烟台大学 | A kind of preparation method and application of high activity fluorine fixing material |
| CN110508293A (en) * | 2019-09-05 | 2019-11-29 | 合肥学院 | A kind of hollow multistage p-n junction NiO@CdS composite nano materials and preparation method thereof for photolysis water hydrogen |
| CN115228874A (en) * | 2022-05-25 | 2022-10-25 | 海南省智慧环境投资控股有限公司 | Dynamic circulation organic solid waste treatment process |
| CN115228874B (en) * | 2022-05-25 | 2023-12-29 | 海南省智慧环境投资控股有限公司 | Dynamic circulation organic solid waste treatment process |
| CN115739121A (en) * | 2022-11-14 | 2023-03-07 | 中国科学院福建物质结构研究所 | Metal-coated composite semiconductor material and preparation method and application thereof |
| CN116713009A (en) * | 2023-06-06 | 2023-09-08 | 常州大学 | Preparation method and application of ZnCdS/NiO composite photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101623645B (en) | 2011-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101623645B (en) | Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition | |
| CN101623644B (en) | Preparation for compound hollow sphere CdS-TiO* and application in photocatalytic hydrogen production by water decomposition | |
| Zhao et al. | Gear-shaped mesoporous NH2-MIL-53 (Al)/CdS PN heterojunctions as efficient visible-light-driven photocatalysts | |
| CN106040216B (en) | A kind of bilayer ZnO hollow ball catalysis materials and preparation method thereof | |
| CN102513134B (en) | Compound photocatalysis material with bismuth sulfide nano particles/bismuth oxychloride and preparation method thereof | |
| Zhao et al. | Cocatalysts from types, preparation to applications in the field of photocatalysis | |
| CN101817562A (en) | Method for preparing hollow spherical Alpha-Fe2O3 by carbon-sugar microsphere template method | |
| CN108452817A (en) | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen | |
| CN103301860B (en) | Preparation method of multiwalled carbon nanotube supported silver phosphate visible light photocatalyst | |
| CN106984337B (en) | CdS-MoS2Nano particle co-doped black porous titanium dioxide photocatalysis agent | |
| CN106268902B (en) | A kind of preparation method of g-C3N4 quantum dot, the quantum dot sensitized BiVO4 photochemical catalyst of Ag | |
| CN109847786A (en) | A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H | |
| CN105833885A (en) | CdS nanorod photocatalyst modified by non-noble metal MoS2 and preparation method and application of CdS nanorod photocatalyst | |
| CN106000474B (en) | A kind of porphyrin/titanium dioxide uniformly organizes the preparation method and applications of nanosphere altogether | |
| CN107737593A (en) | A kind of TiO2The preparation method of nano tube supported bimetallic catalyst | |
| Sun et al. | Plasmonic coupling-boosted photothermal nanoreactor for efficient solar light-driven photocatalytic water splitting | |
| CN108940308A (en) | A kind of preparation of platinum cobalt composition metal photo-thermal catalyst and its application in methane carbon dioxide reformation | |
| CN103599785A (en) | Spinel-supported catalyst for dry reforming of coke oven gas and preparation method thereof | |
| CN106975511A (en) | A kind of MoS2/C60/g‑C3N4Composite photo-catalyst and preparation method thereof | |
| Zhu et al. | Multication and Structure Regulation: Utilizing X‐Doped (X= Co, Mn, Cu) ZnS/CoO Hollow Composites to Spatially Propel the Charge for Superior Solar Hydrogen Evolution | |
| CN105885847A (en) | Cadmium sulphide selenide solid solution quantum dot and preparation method and photocatalytic hydrogen production application thereof | |
| Guan et al. | Engineering tandem double pn heterostructured CeO2@ CdS-Cu8S5 hollow spheres for remarkable photocatalytic CO2 reduction | |
| Liu et al. | Nano-flower S-scheme heterojunction NiAl-LDH/MoS 2 for enhancing photocatalytic hydrogen production | |
| Zhou et al. | Three birds, one-stone strategy for synthesis of hierarchically arrayed defective MnCo2O4@ NF catalyst for photothermal preferential oxidation of CO in H2-rich streams | |
| Zhang et al. | Silica samurai: Aristocrat of energy and environmental catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110126 Termination date: 20110810 |