CN109647445A - A kind of MoS2Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method - Google Patents
A kind of MoS2Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method Download PDFInfo
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- CN109647445A CN109647445A CN201910063881.4A CN201910063881A CN109647445A CN 109647445 A CN109647445 A CN 109647445A CN 201910063881 A CN201910063881 A CN 201910063881A CN 109647445 A CN109647445 A CN 109647445A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910003334 KNbO3 Inorganic materials 0.000 claims abstract description 81
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 70
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 70
- 239000002070 nanowire Substances 0.000 claims abstract description 41
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010955 niobium Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 230000010358 mechanical oscillation Effects 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000005286 illumination Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/39—
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
Abstract
A kind of MoS2Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method, belongs to photocatalysis field.The present invention is with niobium powder (Nb), potassium hydroxide (KOH), sodium molybdate (Na2MoO4·2H2O), thiocarbamide (CN2H4S) it is raw material, by simple two one-step hydrothermal, the good KNbO of crystallinity is made3/MoS2Heterojunction structure piezoelectricity/catalysis material, two one-step hydrothermals refer to that first time hydro-thermal reaction synthesizes KNbO3Nano wire, second of hydro-thermal reaction synthesize KNbO3/MoS2Heterojunction structure piezoelectricity/catalysis material.Preparation method provided by the invention is simple, and experiment condition is easily-controllable, innovatively utilizes piezoelectricity/ferroelectric properties, by promoting the separation of light induced electron and hole, photocatalysis performance is made to obtain largest optimization.The catalytic performance significantly improved is attributed to the synergistic effect of heterojunction structure and the built in field of mechanical oscillation induction promotes the effect of separation of charge.
Description
Technical field
The present invention relates to a kind of MoS2Nanometer sheet coats KNbO3Nano wire hetero structure piezoelectricity/catalysis material preparation side
Method belongs to catalysis material preparation technical field.
Background technique
Photocatalitic Technique of Semiconductor such as Photocatalyzed Hydrogen Production and photocatalysis degradation organic contaminant are to solve world energy sources danger
The method of machine and the great prospect of environmental crisis.A large amount of semiconductor light-catalyst includes metal oxide, metal sulfide, calcium titanium
Mine metal oxide etc. is widely explored.However, light induced electron and the compound of hole strongly limit photocatalysis performance
Raising.For this problem, many method of modifying are for example adulterated, co-catalyst load, nano-structure design etc. are wide
General research.However, the photocatalysis performance of semiconductor light-catalyst is still unsatisfactory.Therefore, it is necessary to seek a kind of energy
The method for effectively facilitating light induced electron and hole separation.
Recent studies have shown that piezoelectricity/ferroelectric material induction built in field can effectively improve photocatalysis performance.Piezoelectricity/iron
Electric material has piezoelectricity/ferroelectric effect, and when external force, built in field generates and promotes light induced electron as a kind of driving force
With the separation and transfer in hole, to improve photocatalysis performance.Various types of piezoelectricity/ferroelectric materials have been applied in light and urge
Change field, such as ZnO, CdS, NaNbO3、BaTiO3And MoS2Deng.However, single piezoelectricity/ferroelectric material nearly all has wide taboo
Band is only capable of absorbing ultraviolet light, strongly limits the raising of catalytic activity.Document shows piezoelectricity/ferroelectric material compound narrow band gap half
Conductor can effectively improve utilization rate to sunlight to construct heterojunction structure photochemical catalyst.
KNbO3It is a kind of typical ferroelectric perovskite oxide, spontaneous polarization generates built in field, and piezoelectric effect makes it
Change the size of built in field in the outer masterpiece used time.In addition, KNbO3With suitable position of energy band and brilliant chemical stabilization
Property, thus attracted the concern of researchers.Due to MoS2Itself has asymmetrical crystal structure, under external force, single
Layer or several layers of MoS2Nanometer sheet has piezoelectric response, and the foundation of built in field drives the separation of light induced electron and hole and turns
It moves, is expected to improve photocatalysis performance.In addition, MoS2Nanometer sheet has brilliant visible light-responded and a large amount of active margin location
It sets, co-catalyst can be played the role of, shift light induced electron and hole, reduce potential barrier.One-dimensional, two-dimensional nanostructure piezoelectricity/
Ferroelectric material is easily-deformable, is also easy to produce piezoelectricity gesture under the effect of external force.Further, since the ultrasonic void effect of ultrasonic wave can generate
Huge stress, and experimentation is simple and easy, so the present invention is using ultrasonic wave as external force source.
So far, KNbO3/MoS2Piezoelectricity/Photocatalyzed Hydrogen Production performance be not reported also.
Summary of the invention
It is an object of the invention to promote the separation of light induced electron and hole in photochemical catalyst, by piezoelectricity/ferroelectric material
Characteristic of semiconductor and piezoelectricity/iron electric polarization combine, and provide a kind of MoS2Nanometer sheet coats KNbO3Nano wire hetero structure piezoelectricity/
The preparation method of catalysis material.
A kind of MoS2Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method, which is characterized in that with niobium
Powder (Nb), potassium hydroxide (KOH), sodium molybdate (Na2MoO4·2H2O), thiocarbamide (CN2H4S it is) raw material, passes through simple two steps water
The good KNbO of crystallinity is made in hot method3/MoS2Heterojunction structure piezoelectricity/catalysis material, the two step hydro-thermals refer to
First time hydro-thermal reaction synthesizes KNbO3Nano wire, second of hydro-thermal reaction synthesize KNbO3/MoS2Heterojunction structure piezoelectricity/photocatalysis
Material.
Further, the preparation method specifically includes the following steps:
(1) first one-step hydrothermal has synthesized KNbO3Nano wire, detailed process is as follows:
It is made into the KOH solution that concentration is 13mol/L with distilled water and KOH first, metal niobium powder, metal niobium powder is then added
Ratio with KOH in solution is 7.5-8.5wt%, magnetic agitation 0.5-1.5h；Finally mixed solution is transferred in reaction kettle,
The temperature for adjusting electric drying oven with forced convection is 140-160 DEG C, time 10-14h；After reacting and terminating and be cooled to room temperature, use
Distilled water and alcohol clean white precipitate repeatedly, and white precipitate is placed in drying box and is dried to obtain KNbO3Nano wire；
(2) second one-step hydrothermals synthesize KNbO3/MoS2Heterojunction structure piezoelectricity/catalysis material, detailed process is as follows:
First by Na2MoO4·2H2O and CN2H4S is dissolved in oxalic acid solution, Na2MoO4·2H2O and CN2H4The ratio of S
Mixed uniformly solution is formed for 1:2, magnetic agitation 25-35min；Therewith, the KNbO that will have been synthesized3Nano wire is placed in
It states in mixed solution, KNbO3Mass concentration of the nano wire in mixed solution is 0.35-0.45g/L, magnetic agitation 0.5-
1.5h；Finally, the temperature for adjusting electric drying oven with forced convection is 180-220 DEG C in the reaction kettle that mixed solution is transferred to, the time
For 22-26h；After reacting and terminating and be cooled to room temperature, precipitating is cleaned repeatedly with distilled water and alcohol, is dried to obtain KNbO3/
MoS2Powder.
Further, in step (1), in white precipitate cleaning process, first wash with distilled water, then it is clear with alcohol
It washes, until the pH of supernatant is 7；Wet-milling drying temperature is 60 DEG C, drying time 12h.
Further, in step (2), the concentration of oxalic acid solution is 0.075mol/L；The dry environment of wet-milling is vacuum, is done
Dry temperature is 60 DEG C, drying time 12h.
The inventive technique design total as one, the present invention also provides a kind of above-mentioned MoS2Nanometer sheet coats KNbO3It receives
The method that the catalysis of rice noodles heterojunction structure produces hydrogen.
Before producing hydrogen test, by the catalyst suspension of 0.2g/L, the H of 0.2mmol2PtCl6·6H2O solution is with 300W's
Xe lamp irradiates 180min, forms the catalyst of platinum (Pt) load, then collects powder sample.Piezoelectricity/Photocatalyzed Hydrogen Production is tested
It is carried out in a closed gas circulation system.Specifically: the 20mg Pt photochemical catalyst loaded is dispersed in containing 15vol.%
Triethanolamine (sacrifice agent) 100mL solution in, using 300W Xe lamp as simulated solar light source, mentioned with ultrasonic washing instrument
For periodical local mechanical stress, hydrogen output is detected with gas chromatograph (Techcomp GC-7900).
The working principle of the invention is:
In the KNbO of preparation3/MoS2In heterojunction structure photochemical catalyst, KNbO3Nano wire and MoS2Nanometer sheet all has larger
Specific surface area, have piezoelectricity/ferroelectric effect.In addition, MoS2With preferable visible light-responded, material visible-light is promoted
It absorbs.
To KNbO3/MoS2After heterojunction structure photochemical catalyst applies external mechanical force, KNbO3In being generated due to iron electric polarization
Electric field is built, enabled band bends.Single layer or several layers of MoS2Nanometer sheet has easily-deformable speciality, under the effect of external force,
Piezoelectricity gesture can be generated, to promote the separation and transfer in light induced electron and hole, the recombination rate of electron hole is reduced, improves catalysis
Performance.
Advantageous effects of the invention:
(1)KNbO3Nano wire and MoS2Nanometer sheet all has biggish specific surface area, can provide for catalysis reaction more
Reactivity site；
(2)MoS2With preferable visible light-responded, the response of material visible-light is promoted；
(3)KNbO3Nano wire and MoS2Nanometer sheet has piezoelectricity/ferroelectric effect, energy under the action of huge mechanical external force
Generate built in field；
(4) built in field that piezoelectricity/iron electric polarization generates can efficiently separate photo-generate electron-hole pair, improve catalytic
Energy.
Detailed description of the invention
Fig. 1 (a) is KNbO3The scanning electron microscope (SEM) photograph of nano wire, Fig. 1 (b) are KNbO3/MoS2Heterojunction structure catalysis material is swept
Electron microscope is retouched, Fig. 1 (c) is MoS2The scanning electron microscope (SEM) photograph of nanometer sheet.
Fig. 2 (a) is KNbO3/MoS2The transmission electron microscope picture of the low resolution of heterojunction structure catalysis material, Fig. 2 (b) are
KNbO3/MoS2The high-resolution transmission electron microscope picture of heterojunction structure catalysis material, Fig. 2 (c) are KNbO3/MoS2Heterojunction structure is urged
Change the selective electron diffraction figure of material.
Fig. 3 (a) is KNbO3The uv-visible absorption spectra of nano wire, Fig. 3 (b) are KNbO3/MoS2Heterojunction structure catalysis
The uv-visible absorption spectra of material, Fig. 3 (c) are MoS2The uv-visible absorption spectra of nanometer sheet.
Fig. 4 (a) is KNbO3Photoluminescence spectra, Fig. 4 (b) of nano wire are KNbO3/MoS2Heterojunction structure catalysis material
Photoluminescence spectra.
Fig. 5 (a) is KNbO3Catalysis H2-producing capacity of the nano wire under simulated solar illumination, Fig. 5 (b) are KNbO3/MoS2It is different
Catalysis H2-producing capacity of the matter structured catalysis material under simulated solar illumination, Fig. 5 (c) are MoS2Nanometer sheet is in simulated solar illumination
Under catalysis H2-producing capacity, Fig. 5 (d) be KNbO3Catalysis of the nano wire under simulated solar illumination and ultrasonic wave collective effect produces
Hydrogen performance, Fig. 5 (e) are KNbO3/MoS2Heterojunction structure catalysis material urging under simulated solar illumination and ultrasonic wave collective effect
Change H2-producing capacity, Fig. 5 (f) is MoS2Catalysis H2-producing capacity of the nanometer sheet under simulated solar illumination and ultrasonic wave collective effect.
Specific embodiment
The present invention cover any substitution made on the essence and scope of the present invention being defined by the claims, modification, etc.
Efficacious prescriptions method and scheme.Further, in order to make the public have a better understanding the present invention, below to datail description of the invention
In, it is detailed to describe some specific detail sections.The description of part without these details for a person skilled in the art
The present invention can be understood completely.
Prepare KNbO3/MoS2Heterojunction structure catalysis material:
(1) first one-step hydrothermal has synthesized KNbO3Nano wire, detailed process is as follows:
It takes 10.942g KOH to be dissolved in the distilled water of 15ml first, is made into the KOH solution that concentration is 13mol/L；Then
The metal Nb powder of 0.874g is added in above-mentioned alkaline solution, magnetic agitation 1h；Mixed solution is finally transferred to 50mL
Reaction kettle in, adjust electric drying oven with forced convection temperature be 150 DEG C, time 12h.To the end of reacting and it is cooled to room temperature
Afterwards, white precipitate is cleaned repeatedly to pH=7 with distilled water and alcohol, and white precipitate is placed in 60 DEG C of dry 12h in drying box.
(2) second one-step hydrothermals synthesize KNbO3/MoS2Heterojunction structure piezoelectricity/catalysis material, detailed process is as follows:
First by the Na of 64.8mg2MoO4·2H2The CN of O and 129.6mg2H4S is dissolved in oxalic acid solution, magnetic agitation
30min forms mixed uniformly solution；Therewith, by the KNbO of the 100mg synthesized3Nano wire is placed in above-mentioned solution, magnetic force
Stir 1h；Finally, mixed solution is transferred in the reaction kettle of 50mL, the temperature for adjusting electric drying oven with forced convection is 200 DEG C, when
Between for for 24 hours.It after reacting and terminating and be cooled to room temperature, is cleaned repeatedly with distilled water and alcohol and is precipitated to pH=7, and white is heavy
Shallow lake is placed in a vacuum drying oven 60 DEG C of dry 12h.
Actual effect of the present invention obtain experiments have shown that.
Fig. 1 (a) is KNbO3The scanning electron microscope (SEM) photograph of nano wire, Fig. 1 (b) are KNbO3/MoS2Heterojunction structure catalysis material is swept
Electron microscope is retouched, Fig. 1 (c) is MoS2The scanning electron microscope (SEM) photograph of nanometer sheet.As shown in Fig. 1 (a), KNbO3Predominantly nano wire pattern is few
Number is the tower-like pattern of micro-meter scale, and the width of nano wire is about 120-400nm, and a length of 2-7 μm, maximum draw ratio reaches 60.This
Outside, KNbO3Surface it is smooth, occasionally have step-like appearance, this is KNbO3It is generated in forming core growth course.KNbO3/MoS2's
SEM figure is as shown in Fig. 1 (b), MoS2Nanometer sheet homoepitaxial is in KNbO3Surface.Fig. 1 (c) is pure MoS2Nanometer sheet microballoon,
Diameter is about 2.8 μm, and nanometer sheet thickness is about 20nm.
Fig. 2 (a) is KNbO3/MoS2The transmission electron microscope picture of the low resolution of heterojunction structure catalysis material, Fig. 2 (b) are
KNbO3/MoS2The high-resolution transmission electron microscope picture of heterojunction structure catalysis material, Fig. 2 (c) are KNbO3/MoS2Heterojunction structure is urged
Change the selective electron diffraction figure of material.The TEM figure of the low resolution of sample is as shown in Fig. 2 (a), MoS2Nanometer sheet is equably grown
In KNbO3The surface of nano wire.Shown in selective electron diffraction figure such as Fig. 2 (c), clearly diffraction spot shows KNbO3Monocrystalline
Essence, and MoS2Due to a large amount of nanometer sheets stacking and produce two fuzzy diffraction rings, correspond to MoS2Nanometer sheet
(100) and (110) crystal face.Shown in high-resolution TEM such as Fig. 1 (b) of sample, 0.404nm and 0.399nm are corresponded respectively to
KNbO3(110) and (001) crystal face, and KNbO3Nano wire is grown along [110] direction.The spacing of lattice of 0.660nm is corresponding
MoS2(002) crystal face.
Fig. 3 (a) is KNbO3The uv-visible absorption spectra of nano wire, Fig. 3 (b) are KNbO3/MoS2Heterojunction structure catalysis
The uv-visible absorption spectra of material, Fig. 3 (c) are MoS2The uv-visible absorption spectra of nanometer sheet.Pure KNbO3It is main to absorb
Ultraviolet portion of the wavelength less than 410nm, ABSORPTION EDGE 418nm, and pure MoS2It can also with brilliant in addition to absorbing ultraviolet light
Light-exposed response.For KNbO3/MoS2, light abstraction width widened visible region, this illustrates to load narrow gap semiconductor MoS2
The optical response range of material can be widened.
Fig. 4 (a) is KNbO3Photoluminescence spectra, Fig. 4 (b) of nano wire are KNbO3/MoS2Heterojunction structure catalysis material
Photoluminescence spectra.With KNbO3It compares, KNbO3/MoS2With lower peak intensity, show KNbO3/MoS2Promote charge carriers
The transfer of son, reduces the compound of photo-generated charge carriers.
Fig. 5 (a) is KNbO3Catalysis H2-producing capacity of the nano wire under simulated solar illumination, Fig. 5 (b) are KNbO3/MoS2It is different
Catalysis H2-producing capacity of the matter structured catalysis material under simulated solar illumination, Fig. 5 (c) are MoS2Nanometer sheet is in simulated solar illumination
Under catalysis H2-producing capacity, Fig. 5 (d) be KNbO3Catalysis of the nano wire under simulated solar illumination and ultrasonic wave collective effect produces
Hydrogen performance, Fig. 5 (e) are KNbO3/MoS2Heterojunction structure catalysis material urging under simulated solar illumination and ultrasonic wave collective effect
Change H2-producing capacity, Fig. 5 (f) is MoS2Catalysis H2-producing capacity of the nanometer sheet under simulated solar illumination and ultrasonic wave collective effect.
Under the irradiation of simulated solar irradiation, KNbO3/MoS2Hydrogen output (305 μm of ol/g) be apparently higher than KNbO3And MoS2Hydrogen output.
Under the collective effect of simulated solar irradiation and ultrasonic wave, the hydrogen generating quantity of all samples increases significantly.KNbO3/MoS2
Hydrogen generation rate reached 573 μm of ol/g, be approximately 1.9 times under simulated solar irradiation.The result shows that ultrasonic activation is to hydrogen
Gas generation plays apparent facilitation.
Claims (6)
1. a kind of MoS2Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method, which is characterized in that with niobium powder
(Nb), potassium hydroxide (KOH), sodium molybdate (Na2MoO4·2H2O), thiocarbamide (CN2H4S it is) raw material, passes through simple two steps hydro-thermal
The good KNbO of crystallinity is made in method3/MoS2Heterojunction structure piezoelectricity/catalysis material, two one-step hydrothermals refer to
One time hydro-thermal reaction synthesizes KNbO3Nano wire, second of hydro-thermal reaction synthesize KNbO3/MoS2Heterojunction structure piezoelectricity/photocatalysis material
Material.
2. MoS as described in claim 12Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method, feature
It is, comprising the following steps:
(1) first one-step hydrothermal has synthesized KNbO3Nano wire, detailed process is as follows:
Be made into the KOH solution that concentration is 13mol/L with distilled water and KOH first, be then added metal niobium powder, metal niobium powder with it is molten
The ratio of KOH is 7.5-8.5wt%, magnetic agitation 0.5-1.5h in liquid；Finally mixed solution is transferred in reaction kettle, is adjusted
The temperature of electric drying oven with forced convection is 140-160 DEG C, time 10-14h；After reacting and terminating and be cooled to room temperature, with distillation
Water and alcohol clean white precipitate repeatedly, and white precipitate is placed in drying box and is dried to obtain KNbO3Nano wire；
(2) second one-step hydrothermals synthesize KNbO3/MoS2Heterojunction structure piezoelectricity/catalysis material, detailed process is as follows:
First by Na2MoO4·2H2O and CN2H4S is dissolved in oxalic acid solution, Na2MoO4·2H2O and CN2H4The ratio of S is 1:2,
Magnetic agitation 25-35min forms mixed uniformly solution；Therewith, the KNbO that will have been synthesized3Nano wire is placed in above-mentioned mixing
In solution, KNbO3Mass concentration of the nano wire in mixed solution is 4.5-5.5g/L, magnetic agitation 0.5-1.5h；Finally, will
In the reaction kettle that mixed solution is transferred to, the temperature for adjusting electric drying oven with forced convection is 180-220 DEG C, time 22-26h；To
After reaction terminates and is cooled to room temperature, precipitating is cleaned repeatedly with distilled water and alcohol, is dried to obtain KNbO3/MoS2Powder.
3. a kind of MoS according to claim 22Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method,
It is characterized in that the pH of cleaning white precipitate to supernatant is 7 in step (1).
4. a kind of MoS according to claim 22Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method,
It is characterized in that drying condition is 60 DEG C, 12h in step (1).
5. a kind of MoS according to claim 22Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method,
It is characterized in that the concentration of oxalic acid solution is 0.075mol/L in step (2).
6. a kind of MoS according to claim 22Nanometer sheet coats KNbO3Nano wire piezoelectricity/catalysis material preparation method,
It is characterized in that in step (2), drying condition are as follows: vacuum drying, 60 DEG C, 12h.
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| CN110773201A (en) * | 2019-05-28 | 2020-02-11 | 江南大学 | Spherical molybdenum disulfide/copper sulfide nanocomposite and preparation method thereof |
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| CN111558384A (en) * | 2020-06-01 | 2020-08-21 | 南昌航空大学 | 2D/2D heterojunction piezoelectric-photocatalyst and preparation method thereof |
| CN112898019A (en) * | 2021-01-28 | 2021-06-04 | 苏州金宏气体股份有限公司 | p-n-KNbO3/Cu2S heterojunction piezoelectric ceramic, preparation method thereof and application of S heterojunction piezoelectric ceramic in self-powered efficient hydrogen production |
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