CN108455658A - Application of the cadmium sulfide two-dimensional nano piece in sound wave assists photocatalytic water hydrogen and oxygen production - Google Patents
Application of the cadmium sulfide two-dimensional nano piece in sound wave assists photocatalytic water hydrogen and oxygen production Download PDFInfo
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- CN108455658A CN108455658A CN201810386570.7A CN201810386570A CN108455658A CN 108455658 A CN108455658 A CN 108455658A CN 201810386570 A CN201810386570 A CN 201810386570A CN 108455658 A CN108455658 A CN 108455658A
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- cadmium sulfide
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- oxygen
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 title claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 30
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000007146 photocatalysis Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910000238 buergerite Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 230000005684 electric field Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000007799 cork Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 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 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006854 communication Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000037230 mobility Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/02—Sulfides
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a kind of application of two-dimentional cadmium sulfide nano piece in sound wave assists photocatalytic water hydrogen and oxygen production, the two dimension cadmium sulfide nano piece is wurtzite crystal structure, belong to noncentrosymmetric crystal, meet the structural condition of piezo-electric crystal, it is orientated special nano-sheet can be by the acoustic wave energy in piezoelectric effect enrichment environment, electric field is generated on nanometer sheet surface, which will promote photo-generated carrier separation, to make it that pure water photocatalysis Decomposition can be promoted to generate hydrogen and oxygen.Cadmium sulfide nano piece of the present invention can split water into hydrogen and oxygen under the collective effect of solar energy and acoustic energy, without adding sacrifice agent, have broad application prospects in Hydrogen Energy field, and preparation method is easy to operate, be suitble to industrialized production.
Description
Technical field
The invention belongs to optoacoustic catalysis technical fields, and in particular to a kind of using in two-dimentional cadmium sulfide nano piece enrichment environment
The acoustic energy of different frequency and then the application for promoting photocatalysis Decomposition pure water hydrogen making and oxygen.
Background technology
Energy shortage is increasingly serious with environmental pollution, it has also become restricts two hang-ups of human society survival and development.It passes
The fossil energy reserves of system are limited, and combustion product is not friendly enough to environment, cannot meet the needs of human social,
Therefore the demand for developing and utilizing clean energy resource is extremely urgent.Hydrogen Energy with it efficiently, cleaning the characteristics of be acknowledged as it is following most
One of energy carrier of potentiality.Nowadays this clean energy resource of solar energy is utilized, selects suitable photochemical catalyst to decompose water and produces
Hydrogen and oxygen, it has also become solve the research hotspot of energy and environmental problem.Realize that photochemical catalyst complete solution water is then ideal
Solution environmental problem effective way.However many photochemical catalyst preparation process complexity, yield is relatively low, Solar use
Rate is low, and most catalyst need the co-catalysts such as carried noble metal, and pure phase catalyst then needs electronics or hole sacrificial mostly
Domestic animal agent is as auxiliary, to realize continuous production hydrogen or production oxygen.
In recent years, people pass through semiconductors coupling, catalyst structure regulation and control, noble metal decorated and applying bias etc.
Means inhibit photo-generated carrier compound and achieve encouraging progress, and the effect of wherein applying bias such as photoelectrocatalysis is outstanding
It is notable.Photoelectrocatalysis can make semiconductor interior lights acoustic-electric that fixed phase separation occur with hole under the action of extra electric field,
So that catalyst surface redox reaction occurs for more carrier mobilities.Extra electric field can be understood as in photocatalytic process
In separately plus it is a kind of promote photo-generated carrier separation energy --- electric energy.It is inspired by this, design is outer based on material self-characteristic
The field auxiliary great foreground of carrier separation means.
It is well known that piezoelectric material is a kind of functional material with non-centrosymmetric structure, and under stress, material
Microdeformation can occur for material, generate polarization phenomena in inside, i.e., generate piezoelectric field in material, therefore, piezoelectric material can be with
The mutual conversion of mechanical energy and electric energy is realized to a certain extent.And sound is the pressure vibration propagated in elastic fluid, sound
Communication process, the also transmittance process of energy.And the energy of this form is widely present in the intensive city of mankind's activity
In.If capturing and being converted into electric energy by the acoustic energy in environment based on the piezoelectric property of material, induces generate in the material
Piezoelectric field will likely can improve the separative efficiency of carrier in photocatalytic process.
Disclosed at home to be produced in hydrogen patent about piezoelectric material, CN106044848A discloses a kind of one-dimensional cadmium sulfide and receives
The preparation method of rice stick piezoelectric material, the one-dimensional cadmium sulfide nano-stick of gained crack aquatic products hydrogen under stress, and production hydrogen process is
Purely mechanic process is not related to chemical process, hydrogen generation efficiency 0.28mL/h/g, and cannot produce oxygen.107537519 A of CN are public
It has opened a kind of cadmium sulfide two-dimensional nano stick array and pure water is decomposed by sound wave assisted photo-catalysis, but sound wave is only limitted to surpass in the patent
Sound wave, and hydrogen and oxygen yield is relatively low.CN106698500A disclose a kind of two-dimentional cadmium sulfide nano piece preparation and its
Application in photochemical catalyzing half-reaction, i.e. photochemical catalyzing under conditions of vulcanized sodium, sodium sulfite do sacrifice agent
Generate hydrogen.
Different from the above-mentioned prior art, the present invention utilizes acoustic energy combination photocatalysis technology, physics based on material itself or
The energy of both low-density of acoustic energy Yu luminous energy is converted to highdensity Hydrogen Energy by chemical effect, is specifically with cadmium sulfide two dimension
Nanometer sheet is catalyst, using the piezoelectricity and photocatalysis property of material itself, realizes the full decomposable process to water and generates hydrogen
With oxygen, essence is chemical process, and realizes the utilization to sound wave in human ear recognizable set, this is in the process without adding
Add sacrifice agent（Sacrifice agent is chemical reagent, and production process necessarily consumes energy and discharge solid, liquid or the waste of gas form）, more
Environment friendly, and hydrogen generation efficiency is up to 7.7ml h-1g-1 W cm-2。
Invention content
The purpose of the present invention is to provide a kind of two-dimentional cadmium sulfide nano pieces in sound wave assists photocatalytic water hydrogen and oxygen production
Using cadmium sulfide photocatalysis property is combined with piezoelectric properties, under conditions of not adding any sacrifice agent, passes through enrichment
Sound wave Assisted Cleavage pure water generates hydrogen and oxygen.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of application of cadmium sulfide two-dimensional nano piece in sound wave assists photocatalytic water hydrogen and oxygen production is comprehensive utilization cadmium sulfide two
The piezoelectric property and photocatalysis performance for tieing up nanometer sheet can promote photocatalysis hydrolysis hydrogen making and oxygen under sound wave effect
Gas.
The frequency of the sound wave is 20Hz-68kHz, and the wavelength of the light is 200nm-700nm.
The cadmium sulfide two-dimensional nano piece is hexagonal crystal system wurtzite-type crystal structure, belongs to non-centrosymmetrical point group,
Its average thickness is 1-3nm, and length is not less than 800nm；Preparation method includes the following steps：
1）In molar ratio 1:5 are scattered in anhydrous caddy with distillation sulphur powder the diethylenetriamine solution of a concentration of 9.12mol/L
In, stirring at normal temperature 30min makes it be uniformly mixed；It is then transferred in reaction kettle, 80 DEG C of insulation reaction 48h, products therefrom difference
It is dry after deionized water, absolute ethyl alcohol washing, obtain hydridization presoma；
2）By step 1）Gained hydridization presoma is scattered in deionized water, and ultrasonic disperse makes it dissolve, and is then stirred back for 80 DEG C
12h is flowed, the organic matter in hydridization presoma is made all to remove, products therefrom is done after deionized water, absolute ethyl alcohol washing respectively
It is dry to get the cadmium sulfide two-dimensional nano piece.
The remarkable advantage of the present invention is：
（1）The crystal structure of two dimension CdS nanometer sheet catalyst of the invention belongs to non-centrosymmetrical hexagonal wurtzite type, meets pressure
The structure feature of transistor, therefore with piezoelectricity；
（2）Compared with other patterns, nano-sheet CdS catalyst is easier to respond acoustic vibration generation piezoelectric effect, therefore more has
Conducive to its enrichment and conversion to acoustic energy；
（3）The present invention uses a step solvent-thermal method, the coordination using crystal seed and diethylenetriamine solvent molecule or chelation tune
The orientation of growth for controlling cadmium sulfide obtains the two-dimensional nano piece of specific morphology structure under suitable reaction temperature and reaction time,
And pure phase cadmium sulfide nano piece is further made by mild water-bath process organics removal；
（4）Gained two dimension CdS nanometer sheets of the invention can auxiliary catalysis photocatalytic water cracking reaction hydrogen making under sound wave effect with
Oxygen, wherein hydrogen generation efficiency is up to 7.7ml h in the ultrasound field of 50kHz-1g-1 W cm-2, hence it is evident that it is higher than other pattern sulphur
Cadmium catalyst, and can realize the utilization to city noise；
（5）The present invention has broken limitation of the cadmium sulfide as traditional photochemical catalyst, has played the piezoelectricity of specific structure cadmium sulfide
Property, acoustic energy that can more effectively in enrichment environment, realize can with while acoustic energy using and mutually reinforcement, urged for light
Agent decomposes pure water hydrogen making and oxygen provides a kind of new approach.
Description of the drawings
Fig. 1 is the X-ray diffractogram of the catalyst synthesized by embodiment 2；
Fig. 2 is the atomic force microscopy diagram spectrum of the catalyst synthesized by embodiment 2；
Fig. 3 is the scantling collection of illustrative plates that the catalyst synthesized by embodiment 2 is obtained by atomic force microscopy diagram spectrum；
Fig. 4 is that the case where catalyst synthesized by embodiment 2 is catalyzed pure water production hydrogen/production oxygen at different conditions is schemed.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The synthesis of 1 two dimension CdS nanometer sheet hydridization presomas of embodiment
The anhydrous caddies of 0.4mmol and 2mmol distillation sulphur powders are weighed, the diethylenetriamine of a concentration of 9.12mol/L is scattered in
In solution, stirring at normal temperature 30min makes predecessor uniformly mix, and is then transferred in reaction kettle, seals, and is put into stainless steel sleeve
Middle locking is warming up to 80 DEG C, keeps the temperature 48h；Gained yellow powder is washed 4-5 times with deionized water and absolute ethyl alcohol respectively respectively,
Dry 12h in 60 DEG C of vacuum drying ovens is transferred to, hydridization precursor samples are obtained.
The synthesis of 2 two dimension CdS nanometer sheets of embodiment
1 gained hydridization precursor samples 40mg of Example, is scattered in 50ml deionized waters, ultrasonic disperse 2min keeps powder molten
Solution, the lower 12h that flows back of 80 DEG C of stirrings, makes the organic matter in hydridization presoma all remove, obtained pale yellow powder is spent respectively
Ionized water and absolute ethyl alcohol wash 3 times respectively, are transferred to 60 DEG C of vacuum drying oven drying 6h, and obtained sample is labeled as CdS-NS.
3 structural characterization of embodiment
The CdS-NS that embodiment 2 synthesizes is scanned using X-ray diffractometer, the result is shown in Figure 1.It can be determined that it is by Fig. 1
Hexagonal wurtzite type CdS crystal.
The CdS-NS that embodiment 2 synthesizes is observed using atomic force microscope, as a result sees Fig. 2,3.By Fig. 2,3 can be with
Find out that gained CdS is two-dimensional nano piece, average thickness is about 1-3 nm, and length is not less than 800nm.
4 two dimension CdS nanometer sheet catalyst photocatalysis pure water hydrogen makings of embodiment and oxygen
Step 1：It takes 2 gained CdS-NS of 10mg embodiments to be respectively placed in the glass reactor that 3 volumes are about 100 mL, adds
Enter 20mL deionized waters, in addition the ground connection with valve, closes connector valve, reaction tube is taken out from mouth of pipe with vacuum pump
Gas, bubble-free bloats again after 30min, closes branch pipe valve and opens connector valve, is filled with high-purity argon gas, turns off connector valve and beat
It pays wages tube valve, vacuumizes, operate 2min every time, be filled with argon gas after 3 times repeatedly, close each valve, fluid sealant closing
Interface, it is spare；
Step 2：It is fixed in the controllable ultrasonic machine of frequency in the above-mentioned reactor equipped with catalyst got ready, with xenon lamp（Power
300W）As simulated solar light source, the water surface is parallel with liquid level in pipe, respectively under illumination condition, under the conditions of acoustic vibration and light+
1h is handled under sound common conditions（50 kHz of frequency of sound wave）, during which remain that recirculated water is in open state to ensure that water temperature is steady
It is fixed；
Step 3：After reaction, it is penetrated from airtight cork with gas sampling needle, extracts gas in 4ml pipes, squeeze into gas-chromatography
In pass through thermal conductivity cell detector（TCD）Detect H2Content converses practical H by known standard curve2With O2Volume；As a result as schemed
4。
From fig. 4, it can be seen that under acoustic vibration and illumination collective effect, CdS-NS degradation waters generate H2With O2Amount highest.
Two dimension CdS nanometer sheet sound cracking pure water hydrogen making and oxygen under the different ultrasonic frequencies of embodiment 5
Step 1：It takes 2 gained CdS-NS of 10mg embodiments to be respectively placed in the glass reactor that 4 volumes are about 100 mL, adds
Enter 20mL deionized waters, in addition the ground connection with valve, closes connector valve, reaction tube is taken out from mouth of pipe with vacuum pump
Gas, bubble-free bloats again after 30min, closes branch pipe valve and opens connector valve, is filled with high-purity argon gas, turns off connector valve and beat
It pays wages tube valve, vacuumizes, operate 2min every time, be filled with argon gas after 3 times repeatedly, close each valve, fluid sealant closing
Interface, it is spare；
Step 2：It is fixed in the controllable ultrasonic machine of frequency in the above-mentioned reactor equipped with catalyst got ready, top applies xenon
Lamp（Power 300W）As simulated solar light source, the water surface is parallel with liquid level in pipe, 1 h of ultrasound behind fixed position, and is applied in lower section
It is respectively 21 kHz, 27kHz, 50kHz, 68kHz to add ultrasonic vibration, frequency of sound wave, during which remains that recirculated water is in and opens
State is to ensure water temperature stability；
Step 3：After reaction, it is penetrated from airtight cork with gas sampling needle, extracts gas in 4ml pipes, squeeze into gas-chromatography
In pass through thermal conductivity cell detector（TCD）Detect H2Content converses practical H by known standard curve2With O2Volume；It the results are shown in Table
1。
1 two dimension CdS nanometer sheets of table are catalyzed the production hydrogen and oxygen-producing amount of photodissociation pure water in different ultrasonic frequencies
By table 1 as it can be seen that two dimension CdS nanometer sheets to be catalyzed photodissociation pure water in different ultrasonic frequencies active, it is two-dimentional in 1 hour
Yield of the CdS nanometer sheets when supersonic frequency is 50 kHz is best, and hydrogen output is about 7.7mlh-1g-1/W·cm-2, produce oxygen
Amount is about 2.6mlh-1g-1/W·cm-2（The volume ratio of hydrogen and oxygen is not 2:1, reason may is that in vibration processes
Generate a large amount of hydrogen peroxide）.
Two dimension CdS nanometer sheets photocatalysis pure water hydrogen making and oxygen under the different noise wave frequency rates of embodiment 6
Step 1：It takes 2 gained CdS-NS of 10mg embodiments to be respectively placed in 3 and is placed in the glass reactor that volume is about 100 mL
In, 20mL deionized waters are added, in addition the ground connection with valve, closes connector valve, air is pumped in the way of embodiment 5
And it is filled with high-purity argon gas；
Step 2：It is fixed in noise generator in the above-mentioned reactor equipped with catalyst got ready, top applies xenon lamp（Power
300W）As simulated solar light source, the interior reaction 4h under conditions of frequency is 3000Hz, 5000Hz, 11000Hz, device
Side be equipped with it is in running order always in fan and reaction process, it is constant with controlling reaction temperature.
Step 3：After reaction, it is penetrated from airtight cork with gas sampling needle, extracts gas in 4ml pipes, squeeze into gas phase
Pass through thermal conductivity cell detector in chromatography（TCD）Detect H2Content converses practical H by known standard curve2With O2Volume；As a result
It is shown in Table 2.
2 two dimension CdS nanometer sheets of table are catalyzed the production hydrogen and oxygen-producing amount of photodissociation pure water in different noise wave frequency rates
As can be seen from Table 2, to be catalyzed photodissociation pure water in different noise frequencies active for two dimension CdS nanometer sheets, it is two-dimentional in 4 hours
Yield of the CdS nanometer sheets when noise frequency is 11000Hz is best, and hydrogen output is about 1.1mlh-1g-1/W·cm-2, produce oxygen
Amount is about 0.23mlh-1g-1/W·cm-2（The volume ratio of hydrogen and oxygen is not 2:1, reason may is that in vibration processes
Generate a large amount of hydrogen peroxide）.
It, can be auxiliary in conjunction with the above content of the test as it can be seen that two dimension CdS nanometer sheets of the invention are under the sound wave effect of different frequency
Photodissociation pure water is helped to generate hydrogen and oxygen.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (4)
1. a kind of application of cadmium sulfide two-dimensional nano piece in sound wave assists photocatalytic water hydrogen and oxygen production, it is characterised in that：The sulphur
Cadmium two-dimensional nano piece can promote photocatalysis hydrolysis hydrogen making and oxygen under sound wave effect.
2. application according to claim 1, it is characterised in that：The frequency of the sound wave is 20Hz-68kHz, the light
Wavelength is 200nm-700nm.
3. application according to claim 1, it is characterised in that：The cadmium sulfide two-dimensional nano piece is hexagonal crystal system buergerite
Type crystal structure, belongs to non-centrosymmetrical point group, average thickness 1-3nm, and length is not less than 800nm；
Preparation method includes the following steps：
1）Anhydrous caddy and distillation sulphur powder are scattered in diethylenetriamine solution, stirring at normal temperature 30min makes it be uniformly mixed；
It is then transferred in reaction kettle, 80 DEG C of insulation reaction 48h obtain hydridization presoma；
2）By step 1）Gained hydridization presoma is scattered in deionized water, and ultrasonic disperse makes it dissolve, and is then stirred back for 80 DEG C
12h is flowed, the organic matter in hydridization presoma is made all to remove to get the cadmium sulfide two-dimensional nano piece.
4. application according to claim 3, it is characterised in that：Step 1）In anhydrous caddy used rub with distillation sulphur powder
You are than being 1:5, a concentration of 9.12mol/L of diethylenetriamine solution used.
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| CN109574066A (en) * | 2018-11-21 | 2019-04-05 | 电子科技大学 | A kind of preparation method and applications of cadmium sulfide nano piece |
| CN110143570A (en) * | 2019-05-24 | 2019-08-20 | 长沙学院 | Application of the two-dimentional zinc sulphide in mechanical catalytic pyrolysis water hydrogen manufacturing |
| CN110975886A (en) * | 2019-12-09 | 2020-04-10 | 西北大学 | Porous two-dimensional zinc cadmium sulfide nanosheet and preparation method and application thereof |
| CN112547125A (en) * | 2020-12-09 | 2021-03-26 | 江南大学 | CdS/NiPc photocatalyst for water photolysis and preparation method thereof |
| CN112624040A (en) * | 2020-12-22 | 2021-04-09 | 佛山(华南)新材料研究院 | Method for preparing hydrogen |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574066A (en) * | 2018-11-21 | 2019-04-05 | 电子科技大学 | A kind of preparation method and applications of cadmium sulfide nano piece |
| CN109574066B (en) * | 2018-11-21 | 2021-03-30 | 电子科技大学 | Preparation method and application of cadmium sulfide nanosheet |
| CN110143570A (en) * | 2019-05-24 | 2019-08-20 | 长沙学院 | Application of the two-dimentional zinc sulphide in mechanical catalytic pyrolysis water hydrogen manufacturing |
| CN110975886A (en) * | 2019-12-09 | 2020-04-10 | 西北大学 | Porous two-dimensional zinc cadmium sulfide nanosheet and preparation method and application thereof |
| CN112547125A (en) * | 2020-12-09 | 2021-03-26 | 江南大学 | CdS/NiPc photocatalyst for water photolysis and preparation method thereof |
| CN112547125B (en) * | 2020-12-09 | 2021-08-24 | 江南大学 | CdS/NiPc photocatalyst for water photolysis and preparation method thereof |
| CN112624040A (en) * | 2020-12-22 | 2021-04-09 | 佛山(华南)新材料研究院 | Method for preparing hydrogen |
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