CN108855186A - A kind of tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation method of S composite photo-catalyst - Google Patents
A kind of tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation method of S composite photo-catalyst Download PDFInfo
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- CN108855186A CN108855186A CN201810644347.8A CN201810644347A CN108855186A CN 108855186 A CN108855186 A CN 108855186A CN 201810644347 A CN201810644347 A CN 201810644347A CN 108855186 A CN108855186 A CN 108855186A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000011701 zinc Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- NDBYHKKGKAWTJG-UHFFFAOYSA-N acetic acid;cadmium;dihydrate Chemical compound O.O.[Cd].CC(O)=O NDBYHKKGKAWTJG-UHFFFAOYSA-N 0.000 claims description 3
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 5
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- -1 ultrasonic 30min Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation of S composite photo-catalyst, including step：Tubular type carbonitride (C3N4) preparation, zinc-cadmium sulfide Cd0.5Zn0.5The preparation of S and tubular type carbonitride (C3N4) doped zinc sulphide cadmium (C3N4@Cd0.5Zn0.5S) the preparation of composite photo-catalyst.The beneficial effects of the invention are as follows：The preparation method is relatively simple, and preparation condition is easy to control, prepared tubular type carbonitride (C3N4) doped zinc sulphide cadmium Cd0.5Zn0.5S composite catalyst has many advantages, such as without secondary pollution, and photocatalysis efficiency is high, has certain application value.
Description
Technical field
The invention belongs to nano material preparation and applied technical fields, are related to a kind of preparing tubular type carbonitride (C3N4)/vulcanization
Zinc cadmium Cd0.5Zn0.5The preparation method of S composite photo-catalyst,.
Background technique
Photocatalysis hydrolysis production hydrogen is a kind of a kind of important means that can make reproducible solar energy hydrogen gas generation, now such as
Extensive concern of the present by researcher.Although having paid huge effort, the huge challenge that current material science faces is out
High-activity photocatalyst is sent out, water is decomposed with low cost.
Class graphite phase carbon nitride (g-C3N4) be novel non-metallic, polymeric material, have high visible absorption intensity and
The forbidden bandwidth of about 2.7eV, compared to traditional conductor photocatalysis material, g-C3N4It has the following advantages that：It is at low cost, acidproof
Alkali, stability is high, easily modified etc..Although g-C3N4It has many advantages, but it is still defective, such as：Relatively low energy
It measures transfer efficiency, lower visible light utilization efficiency and causes poor quantum to be imitated by the Rapid Combination of the electron-hole pair of photogenerated
Rate, the above several points limit g-C3N4Extensive use in photocatalysis.Therefore, the raising of photocatalyst separation efficiency, g-C3N4
The expansion of optical response range and the raising of photocatalytic activity have become g-C3N4Important side of the material in photocatalysis field research
To.Thousand and one way has been used to overcome g-C3N4Inherent defect, including nonmetal doping, metal-doped and building be three-dimensional
Orderly m type macroporous structure and heterojunction structure.In these methods, because of g-C3N4Tubular structure have biggish surface
Product, numerous surface defect and higher separation of charge efficiency, with traditional g-C3N4It compares, it can greatly improve its light and urge
Change activity.
Cd1-xZnxS ternary solid solution, the advantages of having both CdS and ZnS, CdZnS is the promising substitute of CdS, tool
There are preferable anti-light corrosion and visible light-responded ability, is a kind of photocatalysis hydrogen production star catalyst.But Cd1-xZnxS photoproduction
Carrier recombination is still very fast, so by Cd1-xZnxS constructs that form hetero-junctions compound with other semiconductor cocatalyst materials
Object, to Cd1-xZnxS performance optimizes.Design prepares the photocatalysis with high activity and better stability of visible optical drive
Agent can adequately absorb sunlight, become an important subject.
Literature survey discovery, C3N4-Cd0.5Zn0.5The Photocatalyzed Hydrogen Production activity of S nanocomposite is not yet thoroughly studied.This
In we prepare one kind in tubular type carbonitride (C3N4) on the precipitation method load zinc-cadmium sulfide Cd0.5Zn0.5The composite photo-catalyst of S, pipe
Formula carbonitride (C3N4) stability height, using it as research object, the results showed that, prepared C3N4-Cd0.5Zn0.5S is nano combined
Material shows sizable production hydrogen efficiency.Therefore, it is very significant for researching and developing this novel composite photo-catalyst
's.
Summary of the invention
The technical problem to be solved by the present invention is to：Based on the above issues, the present invention provides a kind of tubular type carbonitride (C3N4)/
Zinc-cadmium sulfide Cd0.5Zn0.5The preparation method of S composite photo-catalyst.
The present invention solves a technical solution used by its technical problem：A kind of tubular type carbonitride (C3N4) doping sulphur
Change zinc cadmium Cd0.5Zn0.5The preparation method of S composite photo-catalyst, includes the following steps：
(1)Cd0.5Zn0.5The preparation of S
By Na2The Cd (OAc) containing stoichiometry is added dropwise in S aqueous solution2·2H2O and Zn (OAc)2·2H2O's is water-soluble
In liquid (40mL) (n (Cd)+n (Zn)=0.02mol), it is stirred at room temperature for 24 hours.Then, product is filtered, and uses deionized water
It washs for several times, the dry 5h in 80 DEG C of baking ovens.
(2) tubular type carbonitride (C3N4) preparation
A certain amount of melamine is add to deionized water stirring first, phosphoric acid is then added dropwise dropwise, adjusts pH value.
Continue after stirring a period of time, mixture is transferred in autoclave in 180 DEG C of condition hydro-thermal reaction.Reacted material
Material is then dried in air by centrifuge washing.Dry sample is calcined at high temperature to obtain tubular type carbonitride
(C3N4)。
(3) tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation of S composite photo-catalyst
a:By acetic acid dihydrate cadmium Cd (OAc)2·2H2O and acetic acid dihydrate zinc Zn (OAc)2·2H2It is small that O is put into 100mL
In beaker, 20mL distilled water is added, the tubular type carbonitride (C of certain mass is added to dissolving in stirring at normal temperature 10min3N4), Xiang Rong
1mL dehydrated alcohol is added dropwise in liquid；
b:By anhydrous sodium sulfide Na2S is put into 100mL small beaker, makes it dissolve in 20mL distilled water, and it is molten to draw this with dropper
Liquid instills solution described in a dropwise, is stirred at room temperature for 24 hours.Centrifugation, twice, dehydrated alcohol is washed twice for washing, drying.
Further, Cd (OAc) in the step (1)2·2H2O and Zn (OAc)2·2H2The molar ratio of O is 1：1；
Further, carbonitride (C in the step (2)3N4) pH value be 1；
Further, C in the step (3)3N4:Cd0.5Zn0.5S mass ratio is respectively 2:1,1:1,1:2；
Further, the step (3) conditional temperature is room temperature, and the reaction time is for 24 hours.
Tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The application of S composite catalyst is used for photochemical catalyzing system
Hydrogen carries out as steps described below：
a:Photocatalytic hydrogen production by water decomposition system is divided into light source, and gas generates and collection device three parts, and gas is generated and received
Acquisition means include Photoreactor and gas-circulating system two parts, and the gas analyzing apparatus in photocatalytic hydrogen production by water decomposition system is
Chromatography of gases, target detection thing are hydrogen and oxygen, and chromatographic column selects 5A molecular sieve, and high-purity argon gas (99.999% is selected in carrier gas
Ar).This experiment produces hydrogen storage equipment and is provided by Beijing Bo Feilai Science and Technology Ltd..
b:Under magnetic stirring by composite material tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5S and sacrifice agent vulcanize
Sodium Na2S and sodium sulfite Na2SO3It is dissolved in 100mL deionized water, ultrasonic 30min, particle point is kept using strength magnetic agitation
It dissipates uniformly, is vacuumized to hydrogen reactor is produced, pressure maintaining operation, under xenon lamp irradiation, every 30min automatic sampling is primary, produces hydrogen
Sustained response 3h.The C of different quality ratio is measured with the mole of the generation hydrogen of reaction 3h3N4-Cd0.5Zn0.5S complex light is urged
The Photocatalyzed Hydrogen Production activity of agent.
The beneficial effects of the invention are as follows：The preparation method is relatively simple, and preparation condition is easy to control, prepared tubular type nitrogen
Change carbon (C3N4) doped zinc sulphide cadmium Cd0.5Zn0.5S composite photo-catalyst has many advantages, such as pollution-free, high catalytic efficiency, has one
Fixed application value.
Detailed description of the invention
The following further describes the present invention with reference to the drawings.
Fig. 1 is the tubular type carbonitride (C that the embodiment of the present invention 1 is prepared3N4) transmission electron microscope picture (a), C3N4-
Cd0.5Zn0.5The scanning electron microscope (SEM) photograph (b) and transmission electron microscope picture (c) of S composite photo-catalyst；
Fig. 2 is the tubular type carbonitride (C that the embodiment of the present invention 1 is prepared3N4) doped zinc sulphide cadmium Cd0.5Zn0.5S is compound
The X-ray diffractogram of photochemical catalyst；
Fig. 3 is the tubular type carbonitride (C that the embodiment of the present invention 1 is prepared3N4) doped zinc sulphide cadmium Cd0.5Zn0.5S is compound
Photochemical catalyst produces the activity figure of hydrogen.
Specific embodiment
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
(1)Cd0.5Zn0.5The preparation of S：
By Na2S (1.5608g, 20mmol) is dissolved in 40mL deionized water, is added Cd (OAc)2·2H2O (2.305g,
10mmol) and Zn (OAc)2·2H2In the aqueous solution 40mL of O (1.8348g, 10mmol), it is stirred at room temperature for 24 hours.Then, will
Product filtering, and be washed with deionized for several times, the dry 5h in 80 DEG C of baking ovens.
(2) carbonitride (C3N4) preparation：
The melamine of 8mmol is added in the deionized water of 100mL first and is stirred, phosphoric acid is then added dropwise dropwise, is adjusted
PH value is saved to PH=1.Continue after stirring 30min, mixture is transferred in autoclave in 180 DEG C of condition hydro-thermal reaction
10h.Reacted material is then dried in air by centrifuge washing.Dry sample is calcined to (heating at 500 DEG C
Rate is 2.5 DEG C/min) 4h to obtain carbonitride (C3N4)。
(3) carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation of S composite photo-catalyst
a:By acetic acid dihydrate cadmium Cd (OAc)2·2H2O (0.0953g, 0.4134mmol) and acetic acid dihydrate zinc Zn
(OAc)2·2H2O (0.0758g, 0.4134mmol) is put into 100mL small beaker, and 20mL distilled water, stirring at normal temperature 10min is added
To dissolution, 20mg C is added3N4, to solution in be added dropwise 1mL dehydrated alcohol；
b:By anhydrous sodium sulfide Na2S (0.0645g, 0.8268mmol) is put into 100mL small beaker, makes it dissolve in 20mL
Deionized water in, draw the solution with dropper, dropwise instill a described in solution, be stirred at room temperature for 24 hours.Centrifugation is washed twice,
Dehydrated alcohol is washed twice, drying, and obtaining mass ratio is 1:1 C3N41[Cd0.5Zn0.5S]1。
Scanning electron microscope (SEM) photograph is as shown in Figure 1, as can be seen from Fig., the carbonitride (C of present embodiment preparation3N4) doping vulcanization
Zinc cadmium Cd0.5Zn0.5The pattern of S composite photo-catalyst is that tubular type nitrogenizes supported on carbon surface graininess zinc-cadmium sulfide Cd0.5Zn0.5S, and
It is distributed more uniform.
X ray diffracting spectrum is as shown in Fig. 2, as seen from the figure, the carbonitride (C of preparation3N4) doped zinc sulphide cadmium
Cd0.5Zn0.5S composite photo-catalyst XRD diffraction can be seen in the figure at 27.5 °, 44.8 °, and 53.9 ° zinc-cadmium sulfide occur
Cd0.5Zn0.5S characteristic diffraction peak.Therefore, carbonitride (C can be proved3N4) and zinc-cadmium sulfide Cd0.5Zn0.5S is combined with each other,
And itself crystal form is had not been changed, this is consistent with the result of Electronic Speculum.
(4) light-catalyzed reaction
It is under magnetic stirring 1 by 20mg mass ratio:1 C3N41[Cd0.5Zn0.5S] 1 composite material and vulcanized sodium Na2S
(1.5608g, 20mmol), anhydrous sodium sulfite Na2SO3(3.5291g, 28mmol) is dissolved in 100mL deionized water, ultrasound
30min keeps particle to be uniformly dispersed using strength magnetic agitation, vacuumizes to hydrogen reactor is produced, pressure maintaining operation, in xenon lamp
Under irradiation, every 30min automatic sampling is primary, produces hydrogen sustained response 3h, carries out 6 hydrogen acquisitions.By comparing light reaction 3h's
The mole of hydrogen is generated to measure the Photocatalyzed Hydrogen Production activity of the composite photo-catalyst of different quality ratio.
With above method to different quality ratio (2:1,1:1,1:2) carbonitride/zinc-cadmium sulfide composite photo-catalyst and
Simple C3N4And Cd0.5Zn0.5The production hydrogen activity of S is compared, and as seen from Figure 3, in 3h, hydrogen output has reached volume
7.914mL, 353.3248 μm of ol of mole, it is seen that prepared C3N4@Cd0.5Zn0.5S composite photo-catalyst light with higher
Catalytic activity.
Claims (5)
1. a kind of tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation method of S composite photo-catalyst, which is characterized in that
Include the following steps：
(1)Cd0.5Zn0.5The preparation of S
By Na2The Cd (OAc) containing stoichiometry is added dropwise in S aqueous solution2·2H2O and Zn (OAc)2·2H2The aqueous solution of O
In (40mL) (n (Cd)+n (Zn)=0.02mol), it is stirred at room temperature for 24 hours.Then, product is filtered, and be washed with deionized water
It washs for several times, the dry 5h in 80 DEG C of baking ovens.
(2) tubular type carbonitride (C3N4) preparation
Carbonitride (C3N4) preparation：A certain amount of melamine is add to deionized water stirring first, is then added dropwise dropwise
Phosphoric acid adjusts pH value.Continue after stirring a period of time, mixture is transferred in autoclave in 180 DEG C of condition hydro-thermal
Reaction.Reacted material is then dried in air by centrifuge washing.Dry sample is calcined at high temperature to obtain
Tubular type carbonitride (C3N4)。
(3) tubular type carbonitride (C3N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation of S composite photo-catalyst
a:By acetic acid dihydrate cadmium Cd (OAc)2·2H2O and acetic acid dihydrate zinc Zn (OAc)2·2H2O is put into 100mL small beaker
In, 20mL distilled water is added, the tubular type carbonitride (C of certain mass is added to dissolving in stirring at normal temperature 10min3N4), in solution
1mL dehydrated alcohol is added dropwise；
b:By anhydrous sodium sulfide Na2S is put into 100mL small beaker, makes it dissolve in 20mL distilled water, draws the solution with dropper, by
Drop instills solution described in a, is stirred at room temperature for 24 hours.Centrifugation, twice, dehydrated alcohol is washed twice for washing, drying.
2. a kind of tubular type carbonitride (C according to claim 13N4)/zinc-cadmium sulfide (Cd0.5Zn0.5S) composite photo-catalyst
Preparation method, it is characterized in that：Cd (OAc) in the step (1)2·2H2O and Zn (OAc)2·2H2The molar ratio of O is 1:
1。
3. a kind of carbonitride (C according to claim 13N4)/zinc-cadmium sulfide (Cd0.5Zn0.5S) the system of composite photo-catalyst
Preparation Method, it is characterized in that：Carbonitride (C in the step (2)3N4) pH value be 1；.
4. a kind of carbonitride (C according to claim 13N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation of S composite photo-catalyst
Method, it is characterized in that：NTP in the step (3):Cd0.5Zn0.5S mass ratio is respectively 2:1,1:1,1:2.
5. a kind of carbonitride (C according to claim 13N4)/zinc-cadmium sulfide Cd0.5Zn0.5The preparation of S composite photo-catalyst
Method, it is characterized in that：Conditions Temperature is room temperature, and the reaction time is for 24 hours.
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