CN106076364B - A kind of efficient CdS-CdIn2S4The preparation method of superstructure photochemical catalyst - Google Patents
A kind of efficient CdS-CdIn2S4The preparation method of superstructure photochemical catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 10
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- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 12
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J35/61—Surface area
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Abstract
The invention discloses a kind of efficient CdS nano wires/CdIn2S4The preparation method of the compound superstructure photochemical catalyst of nanometer sheet includes step：1) using cadmium acetate, sodium diethyldithiocarbamate as raw material, ethylenediamine and lauryl mercaptan are mixed solvent, 180 DEG C of solvent thermal reactions, 24 hours synthesis CdS nano wires；2) with the CdS nano wires of preparation, InCl3·4H2O, L cysteine are raw material, and ethylene glycol is solvent, and certain time of flowing back at 200 DEG C synthesizes final products.Product preparation method provided by the invention green, environmental protection, can scale.CdS nano wires/CdIn2S4The compound superstructure of nanometer sheet can be applied to photocatalysis, photoelectrocatalysis decomposes the energy conversions fields such as aquatic products hydrogen.
Description
Technical field
The present invention relates to field of inorganic nano material, and in particular to a kind of efficient CdS-CdIn2S4Superstructure photocatalysis
The preparation method of agent.
Background technology
With the fast development of human society, the demand to fossil fuel resource also increasingly increases.Due to fossil fuel
It is non-renewable, if things go on like this it is bound to cause energy shortage.Meanwhile the CO generated during consumption of fossil fuels2It will cause ring
Border problem.Hydrogen Energy is generally acknowledged clean energy resource, it has nontoxic, and energy density is big, the advantages that having good burning performance.From non-renewable
Hydrocarbon (natural gas, coal, oil) prepare hydrogen, be not the long-term plan of sustainable production hydrogen energy source, and will produce
Pollute the by-products such as carbon dioxide, the carbon monoxide of environment.Water abundance can regenerate, and splitting water is a kind of effective system
Hydrogen means.Sunlight is inexhaustible, utilizes the sunlight of " green ", water hydrogen manufacturing is directly catalytically decomposed, without additional
Energy expenditure, be a kind of ideal hydrogen producing technology.
Currently, photocatalytic hydrogen production by water decomposition technology key problem to be solved is efficient photochemical catalyst exploitation.CdS has
There are suitable conduction band, valence band location, the band gap of 2.4eV that can effectively utilize sunlight.These features make the material non-
Often suitable photochemical catalyzing.However, single, bulk CdS, since specific surface area is small and photo-generated carrier is easily quickly compound,
Photochemical catalyzing H2-producing capacity is poor.On the other hand, CdIn2S4Energy gap about 2.2eV, it is also that a kind of visible light is rung
The photochemical catalyst answered.But it is quick compound due to photo-generated carrier, cause its photocatalysis efficiency also more low.Construct energy band
The hetero-junctions of structure matching can then efficiently separate photo-generated carrier, to improve its photocatalytic activity.
One-dimensional nano structure has the advantages that uniqueness, and the light of such as larger draw ratio, enhancing receives performance, effective current-carrying
Sub- transport efficiency etc., and two-dimensional structure catalysis material has many advantages, such as larger specific surface area and fast transport carrier.Phase
Comparatively, one-dimensional nano structure has relatively small surface area, two-dimensional material to be easy to accumulate.It is super to rationally design one-dimensional/two dimension
Structure can then integrate the two-dimensional geometrical property of a peacekeeping, overcome deficiency existing for single dimension, urged to the light of reinforcing material
Change performance.
Invention content
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of efficient CdS-CdIn2S4The system of superstructure photochemical catalyst
Preparation Method directly synthesizes target product in ethylene glycol that is, using CdS nano wires as raw material by reflux.The material has than table
Area is big, and spectral response range is wide, and it is strong to catch light ability, the advantages that convenient for separation photo-generated carrier, show outstanding photocatalysis,
Photoelectrocatalysis decomposes aquatic products hydrogen activity.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of efficient CdS-CdIn2S4The preparation method of superstructure photochemical catalyst, includes the following steps：
The mixing that cadmium acetate and sodium diethyldithiocarbamate are added sequentially to ethylenediamine and lauryl mercaptan by S1 is molten
In agent, stirs dissolving in 5 minutes and obtain solution；
The finally obtained solution of step S1 is transferred in the autoclave of polytetrafluoroethylliner liner by S2,180 DEG C of conditions
Under reacted；After reaction kettle is cooled to room temperature, alternately washed with water and ethyl alcohol after solid product is centrifuged in solution
After three times, dried within dry 4 hours in 60 DEG C, synthesis obtains CdS nano wires；
The CdS nano wires that S3 will be obtained in step S2, with InCl3·4H2O and L-cysteine together ultrasonic disperse in second
In glycol；
Solution in S4 heating stepses S3 after ultrasonic disperse, is reacted under reflux conditions；Obtained solid product
It is centrifuged, water, ethyl alcohol alternately after washing three times, are dried to get CdS-CdIn for dry 4 hours in 60 DEG C2S4Superstructure light is urged
Agent.
It should be noted that in step S1, cadmium acetate is added and sodium diethyldithiocarbamate mole is respectively
3.5mmol and 7mmol；In step S1, the volume of solvent ethylenediamine and lauryl mercaptan is respectively 102mL and 18mL.
It should be noted that in step S3, CdS nano wires, InCl3·4H2O, the quality of L-cysteine is respectively
120mg, 120mg, 100mg；The volume of ethylene glycol is 100mL.
It should be noted that in step S2, the volume of polytetrafluoroethylliner liner is 150-180mL.
It should be noted that in step S2, the finally obtained solution of step S1 is transferred to the height of polytetrafluoroethylliner liner
After in pressure reaction kettle reaction 24-48 hours is carried out under the conditions of 180 DEG C.
It should be noted that in step S4, the time control reacted under reflux conditions is within 40-60 minutes.
The beneficial effects of the present invention are：
1, the present invention is easy to operate, and all raw material sources are abundant, and method safety is reliable, reproducible, can prepare with scale.
2, products obtained therefrom CdS/CdIn2S4Superstructure, specific surface area with good stability, big, wide spectral response
Range can capture more luminous energy, can efficiently separate photo-generated carrier.
3, by CdS nano wires/CdIn2S4Nanometer sheet superstructure decomposes water for photocatalysis or photoelectrocatalysis, can show
Than single constituent element CdS nano wires, CdIn2S4The better catalytic activity of nanometer sheet has good application prospect.
Description of the drawings
Fig. 1 is the scanning electron microscope (a) and transmission electron microscope picture (b) of CdS nano wires prepared by the present invention.
Fig. 2 is the powder x-ray diffraction style of CdS nano wires prepared by invention.
Fig. 3 is CdS/CdIn prepared by the present invention2S4Scanning electron microscope (a), transmission electron microscope (b) and the high-resolution electricity of superstructure
Mirror image (c).
Fig. 4 is CdS/CdIn prepared by the present invention2S4The powder x-ray diffraction style of superstructure.
Fig. 5 is CdS/CdIn prepared by the present invention2S4The energy dispersive spectrum of superstructure.
Fig. 6 is CdS/CdIn prepared by the present invention2S4The nitrogen Adsorption and desorption isotherms of superstructure and CdS nano wires.
Fig. 7 is CdS/CdIn prepared by the present invention2S4The UV-vis DRS of superstructure and CdS nano wires is composed.
Fig. 8 is CdS/CdIn prepared by the present invention2S4The fluorescence Spectra of superstructure and CdS nano wires.
Fig. 9 is CdS/CdIn prepared by the present invention2S4Superstructure, CdS nano wires, CdIn2S4The hydrogen-producing speed ratio of nanometer sheet
Compared with.
Figure 10 is CdS/CdIn prepared by the present invention2S4Superstructure, CdS nano wires, CdIn2S4Nanometer sheet light anode is being cut
The current -voltage curve of (λ >=420nm) under light irradiation.
Specific implementation mode
Below with reference to attached drawing, the invention will be further described, it should be noted that the present embodiment is with this technology side
Premised on case, detailed embodiment and specific operating process are given, but protection scope of the present invention is not limited to this reality
Apply example.
Embodiment 1
(1) CdS nano wires are synthesized
Clean and sequentially added in dry polytetrafluoroethylliner liner (V=150-180mL) 102mL ethylenediamine,
N- dodecyl mereaptan, 3.5mmol cadmium acetates and the 7mmol sodium diethyldithiocarbamates of 18mL, stirring are allowed to molten in 5 minutes
Solution.By reaction kettle screwing hermetic it is good after be put into electric heating constant-temperature blowing drying box, reacted 48 hours at 180 DEG C.Wait for reaction knot
Cooled to room temperature after beam takes out product, centrifuges, and is washed with absolute ethyl alcohol and removes the organic matter for being attached to surface
Afterwards, then with ethyl alcohol and with high purity water it alternately washs 3 times.Sample products are finally put into vacuum drying chamber, 60 DEG C of dryings 4 hours.
The scanning electron microscope and transmission electron microscope picture for the CdS nano wires that Fig. 1 is.As can be seen from the figure the product is nano thread structure,
About 1.5 μm of length, diameter about 40nm.Fig. 2 is the powder x-ray diffraction style of product, it is all penetrate peak can index turn to six
The cadmium sulfide of square phase, it is consistent with normal data (JCPDS no.41-1049).
(2) CdS/CdIn is synthesized2S4Superstructure
100mL ethylene glycol is added in the three-necked flask (V=250mL) cleaned and dried, the CdS that 120mg has been synthesized receives
Rice noodles, 120mg InCl3·4H2O and 100mg L-cysteine, ultrasonic disperse are uniform.Three-necked flask is placed in 200 DEG C of items again
Oil bath back flow reaction 1h under part.Solid yellow green product is transferred in centrifuge tube and carries out by cooled to room temperature after reaction
It centrifuges, the ethylene glycol for investing surface is washed with absolute ethyl alcohol, then alternately washed 3 times with absolute ethyl alcohol and high purity water.
Final products are put into vacuum drying chamber, 60 DEG C of dryings 4 hours.Fig. 3 a- Fig. 3 c are finally obtained CdS-CdIn2S4Superstructure light
The scanning electron microscope of catalyst and transmission electron microscope picture.It can be seen from the figure that product is the compound superstructure of nano wire and nanometer sheet.
It can be confirmed that nano wire is CdS, nanometer sheet CdIn from high resolution electron microscopy picture2S4.Analyze the powder x-ray diffraction style of product
As a result it shows (Fig. 4), CdS and CdIn is contained in product2S4.It is quantitative (Fig. 5) by power spectrum, CdIn in product2S4With rubbing for CdS
Your ratio is about 8:19.
The performance of product of the present invention is further described below by way of experiment.
Experiment 1
By CdS nano wires and CdS/CdIn2S4Superstructure is respectively in Micromeritics ASAP2020 specific surface areas and hole
Surface area test frequently is carried out on porosity analyzer.The results are shown in Figure 6, CdS/CdIn2S4The ratio of superstructure and CdS nano wires
Surface area is respectively 103cm2/ g and 15cm2/ g, the former is about 6.8 times of the latter.Due to CdIn2S4Nanometer sheet has ultra-thin
Structure increases the specific surface area of composite material.
Experiment 2
By CdS nano wires and CdS/CdIn2S4Superstructure carries out uv drs spectrum test on Shimadzu UV3600 respectively.
The results are shown in Figure 7, CdS/CdIn2S4Superstructure ratio CdS nano wires have stronger absorption, broader spectral response range.By
In CdIn2S4With smaller band-gap energy, the absorption coefficient of bigger causes the composite material to have stronger absorption and broader
Spectral response range.
Experiment 3
By CdS nano wires and CdS/CdIn2S4Superstructure carries out on 4 fluorescence radiation photometers of FluoroMax glimmering respectively
Light spectrum test.The results are shown in Figure 8, and compare CdS nano wires, CdIn2S4The fluorescence peak position of nanometer sheet/CdS nano wires does not have
It changes and intensity is decreased obviously.The fluorescent test the result shows that, CdIn2S4Band structure matched with CdS,
CdIn2S4Hetero-junctions between CdS has efficiently separated photo-generated carrier.Photo-generated carrier efficiently separates, and improves compound
The photocatalysis efficiency and stability of material.
Experiment 4
The experiment that photocatalysis Decomposition aquatic products hydrogen is carried out by on-line checking takes 8.4g Na2S·9H2O and 3.15g
Na2SO3It is dissolved in 100mL high purity waters.It is then transferred in clean and dry 250mL Pyrex reactors,
100mg samples (CdIn2S4/ CdS superstructures, CdS nano wires, CdIn2S4Nanometer sheet) the above-mentioned solution of catalyst addition, stirring is
It is even.Then N is used again2Experiment is exhausted to it, removes the oxygen in suspension, timing half an hour later adds the reactor
Lid sealing, while with detecting system LabSolar H2Photolysis water hydrogen system is attached, and system is evacuated.Pressurize
20min is basically unchanged if registration is in, used using Perfect Light PLS-SXE 300T solar simulators as light source
Edge filter be λ >=420nm.It is 10cm with a distance from flat glass lid of the light source from Pyrex reactors.Single head magnetic force is opened to stir
Device is mixed, and remains stirring in the entire experiment process.It is taken once with gas chromatograph (FULI 9,790 II) per hour
Sample qualitatively and quantitatively analyzes the reaction.The results are shown in Figure 9, CdIn2S4/ CdS superstructures show that optimal production hydrogen is lived
Property.
Experiment 5
FTO sheet glass (size is 1cm × 2cm, thickness 3mm) is respectively surpassed in hydrogen peroxide, ethyl alcohol and high purity water respectively
Sound 20 minutes, then be rinsed with a large amount of deionized waters, weigh the sample (CdIn of 10mg2S4/ CdS superstructures, CdS nano wires,
CdIn2S4Nanometer sheet) it is scattered in the ethylene glycol of 1mL.It takes about 50 μ L mixed liquors uniformly to drop in liquid-transfering gun to have prepared
In FTO glass fronts.60 DEG C of dryings 8 hours are placed it in vacuum drying chamber again.The FTO after drying is finally placed on pipe
It anneals in formula stove, is protected in argon atmosphere, it is 500 DEG C to retract temperature, time 3h.Photoelectrocatalysis decomposes water in electrochemistry work
Make to complete on station CHI-660D (Beijing China Tech Pu Tian scientific ＆ technical corporation), using conventional three-electrode system.Sample/FTO glass is made
For working electrode, platinum electrode is used as to electrode, and calomel electrode is as reference electrode.Configure the Na of 0.05M2S·H2O and 0.05M
Na2SO3The total 100mL of mixed solution, as electrolyte.The test condition of photoelectric current is：Scanning voltage -1.5V~
0.5V, surface sweeping speed 0.01V/s.Light source used is Perfect Light PLS-SXE 300.The tool of being in the light used is
SIHONG AKS-01Z controllor for step-by-step motor.Interval time is 15s.The results are shown in Figure 10, CdIn2S4/ CdS superstructures are aobvious
Show that optimal photoelectrocatalysis decomposes water activity.
For those skilled in the art, it can be made various corresponding according to above technical solution and design
Change and distortion, and all these change and distortions should be construed as being included within the protection domain of the claims in the present invention.
Claims (6)
1. a kind of efficient CdS-CdIn2S4The preparation method of superstructure photochemical catalyst, which is characterized in that include the following steps：
Cadmium acetate and sodium diethyldithiocarbamate are added sequentially to the in the mixed solvent of ethylenediamine and lauryl mercaptan by S1,
Stirring dissolving in 5 minutes obtains solution；
The finally obtained solution of step S1 is transferred in the autoclave of polytetrafluoroethylliner liner by S2, under the conditions of 180 DEG C into
Row reaction；After reaction kettle is cooled to room temperature, alternately washed three times with water and ethyl alcohol after solid product is centrifuged in solution
Afterwards, it is dried within dry 4 hours in 60 DEG C, synthesis obtains CdS nano wires；
The CdS nano wires that S3 will be obtained in step S2, with InCl3·4H2O and L-cysteine together ultrasonic disperse in ethylene glycol
In；
Solution in S4 heating stepses S3 after ultrasonic disperse, is reacted under reflux conditions；Obtained solid product pass through from
The heart detaches, and water, ethyl alcohol alternately after washing three times, are dried to get CdS-CdIn for dry 4 hours in 60 DEG C2S4Superstructure photocatalysis
Agent.
2. preparation method according to claim 1, which is characterized in that in step S1, cadmium acetate and two sulphur of diethyl is added
It is respectively 3.5mmol and 7mmol for carbamic acid sodium mole；In step S1, the volume point of solvent ethylenediamine and lauryl mercaptan
It Wei not 102mL and 18mL.
3. preparation method according to claim 1, which is characterized in that in step S3, CdS nano wires, InCl3·4H2O、L-
The quality of cysteine is respectively 120mg, 120mg, 100mg；The volume of ethylene glycol is 100mL.
4. preparation method according to claim 1, which is characterized in that in step S2, the volume of polytetrafluoroethylliner liner is
150-180mL。
5. preparation method according to claim 1, which is characterized in that in step S2, by the finally obtained solution of step S1
Reaction 24-48 hours is carried out after being transferred in the autoclave of polytetrafluoroethylliner liner under the conditions of 180 DEG C.
6. preparation method according to claim 1, which is characterized in that in step S4, reacted under reflux conditions
Time control is within 40-60 minutes.
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| CN107262115B (en) * | 2017-06-29 | 2019-08-27 | 江苏大学 | A kind of ZnO load C dIn2S4The preparation method and applications of the composite photo-catalyst of nano cubic block |
| CN108315757B (en) * | 2018-01-31 | 2019-10-18 | 温州大学 | Indium sulphur/cadmium sulfide/molybdenum disulfide nano sheet optoelectronic pole preparation and application |
| CN108906080B (en) * | 2018-07-11 | 2020-05-01 | 中国科学技术大学 | CdS/Cu2S/Co-based photoelectric catalytic material and preparation method thereof |
| CN109174123B (en) * | 2018-07-27 | 2020-11-06 | 广东工业大学 | Z-type CdS-Ag-TiO2Composite photocatalytic material and preparation method and application thereof |
| CN109225263B (en) * | 2018-07-27 | 2021-04-23 | 广东工业大学 | CdS/TiO2Nano heterojunction photocatalytic material and preparation method and application thereof |
| CN109092330B (en) * | 2018-08-09 | 2021-03-02 | 齐齐哈尔大学 | CdSQDs@CdIn2S4/CdWO4Preparation of the Material |
| CN109513450B (en) * | 2018-12-07 | 2021-05-25 | 信阳师范学院 | CdS nanotube and spiral CuInS2Heterostructure composite material and preparation method thereof |
| CN110124698B (en) * | 2019-04-30 | 2022-02-15 | 江苏大学 | CdIn2S4Nanoparticle modified few-layer MoS2Preparation method of nanosheet composite photocatalyst |
| CN110639555A (en) * | 2019-10-09 | 2020-01-03 | 长春工业大学 | CdS/CdIn with visible light response2S4Preparation method and application of composite nano-structured photocatalyst |
| CN111139441B (en) * | 2020-03-11 | 2022-02-01 | 鄂尔多斯应用技术学院 | Ti-doped CdIn2S4Intermediate belt film and preparation method thereof |
| CN114887632B (en) * | 2022-05-31 | 2023-07-25 | 青岛科技大学 | Cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst and preparation method and application thereof |
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