CN110075898A - A kind of Photodeposition preparation g-C3N4The method of/CdS composite catalyst - Google Patents
A kind of Photodeposition preparation g-C3N4The method of/CdS composite catalyst Download PDFInfo
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- CN110075898A CN110075898A CN201910324466.XA CN201910324466A CN110075898A CN 110075898 A CN110075898 A CN 110075898A CN 201910324466 A CN201910324466 A CN 201910324466A CN 110075898 A CN110075898 A CN 110075898A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002256 photodeposition Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000003054 catalyst Substances 0.000 title description 11
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 229960004756 ethanol Drugs 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 abstract description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 241000446313 Lamella Species 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 62
- 239000000243 solution Substances 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/399—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
Abstract
The invention discloses a kind of Photodepositions to prepare g-C3N4The method of/CdS composite photo-catalyst, comprising the following steps: g-C is synthesized by the method for melamine thermal polymerization first3N4Nanometer sheet, then being irradiated after having excluded oxygen by light includes sulphur source, cadmium source, g-C3N4Mixed liquor, in g-C3N4The deposition CdS of surface selectivity.The present invention utilizes g-C3N4The reducing power of light induced electron, in g-C3N4Reduction site, CdS is formed in situ.It realizes to CdS in g-C3N4The control accurate of position on lamella.G-C prepared by the present invention3N4/ CdS shows excellent photocatalytic water H2-producing capacity under visible light illumination and performance is recycled.
Description
Technical field
The invention belongs to photocatalytic hydrogen production by water decomposition technical fields, and in particular to a kind of g-C3N4/ CdS hetero-junctions complex light
The method of catalyst.
Background technique
The new method for seeking to solve to cause environmental pollution due to consumption traditional energy is the hot topic of contemporary scientific research.
From Honda-Teng Dao start sex work since, carry out people in the past few decades and pay close attention to semiconductor light-catalyst always.Semiconductor light is urged
Change one of the attractive mode that water decomposition is clean energy resource production.In order to effectively utilize solar energy, it is highly desirable to which light is urged
Agent has excellent visible light activity, high charge separative efficiency and excellent photostability.
Recently, graphitic nitralloy carbon (g-C3N4) received significant attention as a kind of novel visible photochemical catalyst, because they
It is readily synthesized, and band gap relative narrower (~2.7ev).By g-C3N4It couples to form heterojunction structure not only with narrow gap semiconductor
The absorption of visible light region can be expanded, the separation of photohole and electronics can also be promoted, greatly improve photocatalysis efficiency.And
CdS has narrow band gap (~2.2ev), can absorb the up to sunlight of 560nm, to be catalyzed the half-reaction release of water decomposition
Hydrogen.Meanwhile CdS has good carrier transport ability, can timely and effectively make light induced electron and hole mobile.
Currently, having made to synthesize the CdS base semiconductor nano material with required structure in many ways to realize that height is urged
Change efficiency.But CdS how is accurately adjusted in g-C3N4On position and partial size simultaneously with easy scheme control CdS it is seldom
It is studied and to design synthesis difficulty larger.For this problem, the present invention proposes heavy using a kind of mild quickly photochemistry
Long-pending mode can regulate and control CdS in g-C3N4Load situation in nanometer sheet, and CdS size dimension has also obtained good control
System.
Summary of the invention
It is an object of the invention to solve problems of the prior art, and provide a kind of Photodeposition preparation g-C3N4/
The method of CdS composite photo-catalyst enables the method to accurately adjust CdS in g-C3N4On position and simultaneously with easy
The partial size of scheme control CdS
Inventive concept of the invention is: synthesizing g-C by the method for melamine thermal polymerization first3N4Then nanometer sheet is led to
Crossing light and irradiating after having excluded oxygen includes sulphur source, cadmium source, g-C3N4Mixed liquor, in g-C3N4Surface selectivity is sunk
Product CdS.
The present invention is realized especially by following technology:
A kind of Photodeposition preparation g-C3N4The method of/CdS composite photo-catalyst, comprising the following steps:
1) ontology g-C is synthesized by the method for melamine thermal polymerization3N4；
2) by ontology g-C obtained in step 1)3N4By hot soarfing from method be prepared into g-C3N4Nanometer sheet
3) by g-C obtained in step 2)3N4Nanometer sheet, which is dissolved in dehydrated alcohol, obtains g-C3N4Mixed liquor, then to g-
C3N4It is separately added into cadmium nitrate in mixed liquor and sedimentation sulphur obtains reaction solution；
4) after reaction solution obtained in step 3) being excluded oxygen, it is placed in 1~5h of irradiation under xenon lamp, is made by Photodeposition
CdS is in g-C3N4Surface selective deposition, obtains g-C3N4/ CdS material obtains g-C after dry through over cleaning3N4/ CdS is compound
Photochemical catalyst.
In this scenario, the design parameter of each step and way can be realized using following preferred embodiment.
Preferably, the g-C3N4Nanometer sheet the preparation method comprises the following steps: firstly, passing through the method for melamine thermal polymerization
Synthesize ontology g-C3N4；Again by ontology g-C3N4By hot soarfing from method be prepared into g-C3N4Nanometer sheet.
Further, the g-C3N4Nanometer sheet the preparation method comprises the following steps: melamine is placed in Muffle furnace, with 2.3
DEG C/heating rate of min, 550 DEG C are warming up to, and keep 4h, obtain ontology g-C3N4；Take ontology g-C3N4It is placed in Muffle furnace,
With the rate of 5 DEG C/min, 500 DEG C are warming up to, 2h is kept, obtains g-C3N4Nanometer sheet.
Preferably, in the reaction solution, g-C3N4: sedimentation sulphur: the mass ratio of cadmium nitrate is 200mg:64mg:
1.23g, the volume of dehydrated alcohol are 200ml.
Preferably, being continually fed into nitrogen during entire light deposition.
Preferably, the xenon lamp is 300W xenon lamp.
Preferably, irradiation time of the reaction solution under xenon lamp is preferably 4h.
Preferably, the cleaning method are as follows: g-C will be contained3N4The mixed liquor of/CdS material is centrifuged, right
It is centrifuged obtained solid ethyl alcohol and deionized water repeated flushing, washes away unreacted raw material.Further, it is centrifugated revolving speed
For 4000r/min, retention time 5min.Further, repeated flushing number > 10 time.
Preferably, described dry using baking oven drying mode, the temperature of baking oven remains 60 DEG C, drying time > 8h.
Preferably, the amount of melamine is 10g in step 1).
Preferably, in step 4), the method that excludes oxygen are as follows: it is continually fed into nitrogen into reaction solution and is stirred continuously,
Duration is preferably 1h.
A kind of Photodeposition of the present invention prepares g-C3N4The method of/CdS composite photo-catalyst, with existing technology
It compares, has the advantage that
(1) present invention utilizes g-C3N4The reducing power of light induced electron, in g-C3N4Reduction site, CdS is formed in situ,
It realizes to CdS in g-C3N4The regulation of position on lamella.Therefore the preparation method of the composite catalyst, the deposition position of CdS are used
Point can be regulated and controled, and size is controlled, and preparation method is simple and convenient.
(2) there is the composite catalyst excellent visible light-responded property to show excellent light in terms of photodegradation water
Water H2-producing capacity is solved, and has the characteristics that stability is high.
Detailed description of the invention
Fig. 1 is g-C3N4The scanning electron microscope (SEM) photograph of nanometer sheet.
Fig. 2 is the scanning electron microscope (SEM) photograph of pure CdS.
Fig. 3 is g-C3N4The scanning electron microscope (SEM) photograph of/CdS composite photo-catalyst CS-4.
Fig. 4 is g-C3N4(scale from top to bottom is followed successively by the images of transmissive electron microscope of/CdS composite photo-catalyst CS-4
100nm, 20nm and 5nm).
Fig. 5 is C3N4The STEM-EDX element distribution image of/CdS composite photo-catalyst CS-4.
Fig. 6 is the X ray diffracting spectrum (XRD) of the sample CS-T of different light application times preparation.
Fig. 7 is the H2-producing capacity figure of the sample of preparation.A is the sample H2-producing capacity figure of different light application times preparation, b g-
C3N4Nanometer sheet, pure CdS, CS-4 H2-producing capacity figure, c are the experiment that CS-4 produces stabilized hydrogen, and d is that separation sample obtains after producing hydrogen 55h
The XRD spectra arrived.
Fig. 8 is that the sample of preparation carries out the TEM picture after Pt sedimentation experiment.A is to carry out the spectrogram that line is swept to selection area,
B is the high-resolution picture of selection area.
Specific embodiment
With reference to embodiments, it elaborates to the present invention, but protection scope of the present invention is not limited to following embodiments,
I.e. in every case with simple change made by scope of the present invention patent and description, all category protection scope of the present invention.
Embodiment 1
In the present embodiment, Photodeposition prepares g-C3N4The method and step of/CdS composite photo-catalyst is as follows:
(1) ontology g-C3N4Preparation
It weighs 10g melamine to be placed in crucible, be transferred in Muffle furnace, be warming up to the heating rate of 2.3 DEG C/min
550 DEG C, and 4h is kept, obtain ontology g-C3N4；
(2)g-C3N4The preparation of nanometer sheet
By ontology g-C obtained in step (1)3N4Powder is placed in crucible, in Muffle furnace, with the heating speed of 5 DEG C/min
Rate is warming up to 500 DEG C, and keeps 2h, and g-C is prepared3N4Nanometer sheet；
(3)g-C3N4The synthesis of/CdS
By g-C obtained in step (2)3N4Nanometer sheet 200mg is added in 200ml dehydrated alcohol, and ultrasonic disperse is uniform to be obtained
To g-C3N4Mixed liquor, then to g-C3N4It is separately added into 1.23g cadmium nitrate and 64mg sedimentation sulphur in mixed liquor, is uniformly mixed
To reaction solution.It is continually fed into nitrogen into gained reaction solution and stirs, 1h is kept, so that the oxygen in reaction solution is excluded.It will
Reaction solution after excluding oxygen is placed in the different time irradiated under 300W xenon lamp (Quan Guangpu) 1~5 hour, in irradiation process according to
So persistently keep being passed through for nitrogen.
(4)g-C3N4The cleaning of/CdS material
Mixed solution obtained in step (3) is placed in centrifuge tube and is centrifugated, revolving speed 4000r/min, when holding
Between 5min.After centrifugation, bottom sediment is collected with ethyl alcohol, deionized water repeated flushing 10 times and washes away unreacted original
Material；
(5)g-C3N4The drying of/CdS material
By g-C in step (4)3N4/ CdS particle dries drying in an oven, and the temperature of baking oven remains 60 DEG C, when drying
Between > 8h to get arrive g-C3N4/ CdS composite photo-catalyst.
In the present embodiment, g-C that different xenon lamp irradiation times obtains3N4/ CdS composite photocatalyst sample is labeled as CS-
T, T=1,2,3,4,5.Such as CS-4, indicate the sample of light deposition 4h preparation.
In addition, showing the g-C to compare3N4The effect of/CdS composite photo-catalyst, the present embodiment are also prepared for pure CdS.
Pure CdS's the preparation method comprises the following steps: using ultrasonic treatment by cadmium nitrate (8mmol), thiocarbamide (TU8mmol) and polyvinylpyrrolidone
(PVP；It 0.9g) is dissolved in 80mL deionization (DI) water.The homogeneous mixture of acquisition is transferred to the stainless steel of Teflon lining
It is kept for 12 hours in autoclave (100mL) and in electric furnace at 160 DEG C.After cooled to room temperature, by being collected by centrifugation
Product with ethyl alcohol and distills water washing for several times, finally 10 hours dry at 80 DEG C in air.
After the completion of preparation, to the g-C of above-mentioned preparation3N4G-C in/CdS, pure CdS sample and preparation step (2)3N4,
The characterization of pattern is carried out, obtained Measurement results are as shown in Figure 1.
As shown in Figure 1, pure g-C3N4After Overheating Treatment, typical 2D lamellar structure, sheet surfaces light are shown
It is sliding.As shown in Fig. 2, the surface topography of pure CdS shows the phenomenon that serious little particle stacking.Fig. 3 shows CS-4's
Surface topography, it can be seen that CdS nano particle is evenly distributed in g-C3N4Surface, size be lower than 20nm, this has been with Fig. 2
Complete different existing way.Fig. 4 is the transmission electron microscope picture of CS-4, it can be seen that CdS exposes from the bottom f figure of Fig. 4
(002) and (101) crystal face.Fig. 5 is the distribution diagram of element of CS-4, it can be seen that C, N, S, Cd are uniformly distributed.
Comparative example 1
In this comparative example, g-C3N4/ CdS composite photo-catalyst is substantially the same manner as Example 1, and difference is only that step (3)
Middle synthesis g-C3N4When/CdS, solvent replaces with deionized water by dehydrated alcohol, and sulphur source replaces with thiocarbamide by sedimentation sulphur, remaining
Step way is all the same.But in this comparative example, the compound of glassy yellow is not obtained, is shown finally without generating g-C3N4/
CdS composite photo-catalyst.
Embodiment 1 is compared with comparative example 1, it can be seen that the influence of dehydrated alcohol and sedimentation sulphur to present invention preparation result.
In synthesis process of the invention, g-C3N4By the irradiation of sunlight in ethanol solution, electrons and holes can be inspired,
And hole can be captured by ethanol solution, the electronics of generation, and the excessive divalent cadmium ion in solution can be reduced to zeroth order cadmium,
And then cadmium sulfide is generated with the sedimentation reaction of Salmon-Saxl in solution.And in the aqueous solution of comparative example, similarly g-C3N4 can be by
To the excitation of sunlight, generate hole and electronics, but the more inertia of thiocarbamide, and the solvability of aqueous solution itself also compared with
Difference, the active material of generation can not convert thiocarbamide and cadmium nitrate to cadmium sulfide, thus reaction excessively can not slowly synthesize it is compound
Catalyst.
Embodiment 2
By g-C obtained in the present embodiment 13N4/ CdS composite photo-catalyst CS-T carries out X-ray powder diffraction, and same
When to the g-C in embodiment 13N4X-ray diffraction is carried out with pure CdS.Obtained XRD diffracting spectrum is compared, such as Fig. 6 institute
Show, the crystal diffraction peak and g-C of CS-43N4Corresponding with the crystal diffraction peak of CdS, the appearance at free from admixture peak illustrates g-C3N4With
Both CdS, which are formd, good compound urges agent.
Embodiment 3
By g-C preparation-obtained in the present embodiment 13N4/ CdS composite photo-catalyst CS-T carries out photodissociation aquatic products hydrogen
Experiment, tests the performance of its Photocatalyzed Hydrogen Production, the specific method is as follows:
The CS-T of 20mg is weighed, 10ml lactic acid is added as agent solution is sacrificed into 90ml water in ultrasonic disperse, is put into light
Chemically react in instrument, vacuumize half an hour, turn on light (300W Xe lamp wavelength is > 420nm) carry out producing hydrogen test, and timing is logical
Cross gas-chromatography (MS-5A molecular sieve, TCD, N2For carrier gas) measure the yield for generating hydrogen.
As shown in Figure 7a, start the extension of the time prepared with light deposition, hydrogen output is obviously improved, and works as light deposition
When the time of preparation is 4h, hydrogen output reaches highest.When extending light application time again, hydrogen output is declined, this may be to generate
CdS stacking influence.As shown in Figure 7b, CS-4 sample shows excellent H2-producing capacity, considerably beyond CdS and g-C3N4's
Produce hydrogen.
Embodiment 4
The g-C that will be prepared in embodiment 13N4/ CdS composite photo-catalyst CS-4 sample carries out the duplicate test for producing hydrogen,
The specific method is as follows:
The CS-4 of 20mg is weighed, 10ml lactic acid is added as agent solution is sacrificed into 90ml water in ultrasonic disperse, is put into light
Chemically react in instrument, vacuumize half an hour, turn on light (300W Xe lamp wavelength is > 420nm) carry out producing hydrogen test, and timing is logical
Cross gas-chromatography (MS-5A molecular sieve, TCD, N2For carrier gas) measure the yield for generating hydrogen
It using 5h as a cycle, after each reaction, is vacuumized with vacuum pump, the circulation carried out again of turning on light, every time
Agent solution is sacrificed without supplementing when circulation, 40h supplements 1ml and sacrifices agent solution.After reacting 55h, reaction is collected by centrifugation
CS-4 sample afterwards, is repeatedly rinsed with deionized water and ethyl alcohol, is placed in baking oven and dries.Obtain CS-4 sample after reaction
Product carry out XRD analysis.
As shown in Figure 7 c, CS-4 shows excellent stability, within the reaction time of 55h, can keep very high steady
It is qualitative.The crystal structure that CS-4XRD analysis after the completion of reaction can be seen that CS-4 does not find significantly to change, this
Show that CS-4 is a kind of stable catalyst, prolonged stability can be kept, and there is excellent visible light H2-producing capacity.
Above-mentioned embodiment is only a preferred solution of the present invention, so it is not intended to limiting the invention.Have
The those of ordinary skill for closing technical field can also make various changes without departing from the spirit and scope of the present invention
Change and modification.Therefore all mode technical solutions obtained for taking equivalent substitution or equivalent transformation, all fall within guarantor of the invention
It protects in range.
Embodiment 5
The g-C that will be prepared in embodiment 13N4/ CdS composite photo-catalyst CS-4 sample carries out Pt deposition test, specific side
Method is as follows:
The CS-4 of 20mg is weighed, 10ml lactic acid is added as sacrificing agent solution and appropriate into 90ml water in ultrasonic disperse
Platinum acid chloride solution (1wt% that control Pt deposition is CS-4) is put into photochemical reaction instrument, is vacuumized half an hour, is turned on light
(300W Xe lamp wavelength is > 420nm) irradiates 30min.Sample is collected by way of centrifugation, is placed in 60 DEG C of baking oven and is done
It is dry overnight.
In general, in illumination raCl platinic acid and g-C3N4Mixed liquor when, Pt can be deposited on g-C3N4Electronics be precipitated position
Point on.It, can be with the site of electronics on indirect proof g-C3N4 point so by judging position of the Pt on composite catalyst CS-4
Cloth situation.Mode (Fig. 8 a) is swept by the line of transmission electron microscope, we can be clearly seen that, the Elemental redistribution of Pt is and Cd, S member
Element distribution is consistent, and does not appear in g-C3N4This shows that Pt is mainly deposited on the surface of CdS, so that it is heavy to demonstrate CdS
Long-pending position is in g-C3N4Electronically active site on.Can also be visible in detail from the transmission electron microscope picture of Fig. 8 b, Pt's
Lattice fringe also occurs from the lattice fringe attachment of CdS, this has also further demonstrated that the g-C that the position of CdS occurs from3N4
Electronics be precipitated site on.It can be seen that Photodeposition of the invention prepares g-C3N4When/CdS composite photo-catalyst, CdS is in g-
C3N4Area load can carry out selective regulation.
Claims (10)
1. a kind of Photodeposition prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that the method includes following
Step: 1) by g-C3N4Nanometer sheet, which is dissolved in dehydrated alcohol, obtains g-C3N4Mixed liquor, then to g-C3N4Add respectively in mixed liquor
Enter cadmium nitrate and sedimentation sulphur obtains reaction solution；
2) after reaction solution obtained in step 1) being excluded oxygen, it is placed in 1~5h of irradiation under xenon lamp, CdS is made by Photodeposition
In g-C3N4Surface selective deposition, obtains g-C3N4/ CdS material obtains g-C after dry through over cleaning3N4/ CdS complex light is urged
Agent.
2. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that institute
The g-C stated3N4Nanometer sheet the preparation method comprises the following steps: firstly, synthesizing ontology g-C by the method for melamine thermal polymerization3N4；Again will
Ontology g-C3N4By hot soarfing from method be prepared into g-C3N4Nanometer sheet.
3. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that institute
In the reaction solution stated, g-C3N4: sedimentation sulphur: the mass ratio of cadmium nitrate is 200mg:64mg:1.23g, and the volume of dehydrated alcohol is
200ml。
4. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that whole
Nitrogen is continually fed into during a light deposition.
5. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that institute
Stating xenon lamp is 300W xenon lamp.
6. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that anti-
Answering irradiation time of the liquid under xenon lamp is preferably 4h.
7. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that institute
The cleaning method stated are as follows: g-C will be contained3N4The mixed liquor of/CdS material is centrifuged, the solid ethyl alcohol obtained to centrifugation
With deionized water repeated flushing, unreacted raw material is washed away.
8. Photodeposition as claimed in claim 7 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that from
It is 4000r/min, retention time 5min that the heart, which separates revolving speed,.
9. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that step
It is rapid 4) in, the method that excludes oxygen are as follows: be continually fed into nitrogen into reaction solution and be stirred continuously, the duration is at least 1h.
10. Photodeposition as described in claim 1 prepares g-C3N4The method of/CdS composite photo-catalyst, which is characterized in that institute
Drying is stated using baking oven drying mode, the temperature of baking oven remains 60 DEG C, drying time > 8h.
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