CN105562037B - A kind of copper and tin sulphur engraved structure micron ball and preparation method and application - Google Patents
A kind of copper and tin sulphur engraved structure micron ball and preparation method and application Download PDFInfo
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- CN105562037B CN105562037B CN201510876407.5A CN201510876407A CN105562037B CN 105562037 B CN105562037 B CN 105562037B CN 201510876407 A CN201510876407 A CN 201510876407A CN 105562037 B CN105562037 B CN 105562037B
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- copper
- engraved structure
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- 239000010949 copper Substances 0.000 title claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910020628 SiW12O40 Inorganic materials 0.000 claims abstract description 10
- 239000012488 sample solution Substances 0.000 claims abstract description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 4
- 239000001119 stannous chloride Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 12
- 229940043267 rhodamine b Drugs 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000006303 photolysis reaction Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 17
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910020994 Sn-Zn Inorganic materials 0.000 description 2
- 229910009069 Sn—Zn Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000009021 linear effect Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
-
- 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
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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)
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- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of copper and tin sulphur engraved structure micron ball of disclosure of the invention and preparation method and application, a diameter of 10 ~ 15 μm of the copper and tin sulphur structure micron ball, micron spherome surface are in porous geometric configuration, and aperture is 1 ~ 3nm, and hole depth is 1 ~ 3nm.Preparation method includes the following steps：By raw material copper chloride, stannous chloride, thiocarbamide and K4SiW12O40According to 1:1:3:10‑3Molar ratio be dissolved in ethylene glycol and form sample solution, carry out being thermally treated resulting in object copper and tin sulphur engraved structure micron ball.Using the application for the copper and tin sulphur engraved structure micron ball in photochemical catalyst is prepared.The preparation method of the present invention is easy to operate and in light degradation rhodamine B（RhB）Photodissociation and photocatalytic hydrogen production by water decomposition in terms of show very strong catalytic effect.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of copper and tin sulphur engraved structure micron ball and preparation method thereof with
Using.
Background technology
In recent years, the continuous rising of sustainable industrial expansion and population support, lead to human society to energy demand
Continue to increase, traditional energy is non-renewable and almost exhausted, and global range is faced with increasingly severeer energy crisis, this
A little problems all drive us to look for environmental-friendly reproducible novel energy.Solar energy be considered as one kind take no
To the greatest extent, the nexhaustible energy, disclosure satisfy that the growing energy demand of following human society.However, intermittent sun spoke
Penetrating and lacking cost-effective energy stores method becomes the most important challenge for utilizing solar energy.Since Fujishima and Honda
It was found that since light radiation can drive the titanium dioxide hydrogen production by water decomposition of light anode, photocatalytic hydrogen production by water decomposition becomes greenization
Most potential storage solar energy method, people have carried out systematic research, such as ZnO to a large amount of semi-conducting material in,
BiVO4, WO3, SrTO3, NaNbO3And Ga2O3Deng.However, these materials are mostly since their band gap are wide and serious electricity
Son-hole pair it is compound cause it is inefficient.
In face of these problems, the sight of people is stepped into chalcogenide materials, not only due to it is with high visible
Light absorptivity（More than 10-4 cm-1）With ideal band gap magnitude（1.4-1.6eV）, and the newest fruits in the field show
CTS has the degradation hydrogen production activity of potential water and pollutant, it is even more important that new functional material is introduced into CTS,
Such as CTS- metals（Au or Pt）CTS can be made to show higher photocatalytic activity.These breakthroughs, which are undoubtedly, to be set up
Bridge between opto-electronic conversion and photocatalysis, while also started the new upsurge that CTS is applied in photocatalysis field.
Invention content
The first object of the present invention is to provide a kind of copper and tin sulphur engraved structure micron ball；Second be designed to provide it is described
Copper and tin sulphur engraved structure micron ball preparation method；Third is designed to provide the copper and tin sulphur engraved structure micron ball
Using.
The first object of the present invention is achieved in that a diameter of 10-15 μm of the copper and tin sulphur structure micron ball, micron
Spherome surface is in porous geometric configuration, and aperture is 1 ~ 3nm, and hole depth is 1 ~ 3nm.
The second object of the present invention, which is achieved in that, to be included the following steps：
A, by raw material copper chloride, stannous chloride, thiocarbamide and K4SiW12O40According to 1:1:3:10-3Molar ratio be dissolved in
Sample solution is formed in ethylene glycol；
B, sample solution is carried out being thermally treated resulting in object copper and tin sulphur engraved structure micron ball.
The third object of the present invention is achieved in that the copper and tin sulphur engraved structure micron ball is preparing photochemical catalyst
In application.
Polyanionic is introduced into CTS systems and obtains engraved structure by the present invention（It is porous）CTS micron balls, i.e. copper and tin sulphur mouth
Hollow structure micron ball has porous geometric configuration on the copper and tin sulphur mouth hollow structure micron ball, integrally seems and " aerolite
The structure in hole " is similar, and micron ball is 10-15 microns a diameter of, the characteristic for have large specific surface area, not reuniting, preparation method operation
Simply and in light degradation rhodamine B（RhB）Photodissociation and photocatalytic hydrogen production by water decomposition in terms of show very strong catalytic effect.
Description of the drawings
Fig. 1 is CTS-POM XRD spectras；
Fig. 2 is CTS-POM XPS spectrum figures；
Fig. 3 is the electron microscope of the asynchronous CTS-POM of polyacid content（A-d, polyacid content are respectively 1 ~ 5%）；
Fig. 4 is is not added with obtained CTS electron microscopes in the case of POM；
The TEM that Fig. 5 is CTS-POM schemes；
Fig. 6 is CTS-POM ultraviolet-ray visible absorbing figures；
Fig. 7 schemes for CTS-POM photocatalytic degradations rhodamine B；
Fig. 8 is CTS-POM photocatalysis hydrogen production figures；
Fig. 9 is possible CTS-POM photocatalytic mechanisms figure.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is further illustrated, but the present invention is not subject in any way
Limitation, based on present invention teach that any transformation or replacement made, all belong to the scope of protection of the present invention.
Copper and tin sulphur engraved structure micron ball of the present invention, a diameter of 10-15 μm, micron spherome surface is in porous several
What configuration, aperture are 1 ~ 3nm, and hole depth is 1 ~ 3nm.
The x-ray diffractogram of powder of the copper and tin sulphur engraved structure micron ball is composed at 28.72 °, 32.79 °, 47.73 °,
Characteristic diffraction peak is shown at 56.33 °, 69.38 ° and 76.72 ° of 2 θ ± 0.1 ° angles of reflection.
The preparation method of copper and tin sulphur engraved structure micron ball of the present invention, includes the following steps：
A, by raw material copper chloride, stannous chloride and thiocarbamide 1:1:It is molten that 3 molar ratio is dissolved in formation sample in ethylene glycol
Liquid；
B, K is added in into sample solution4SiW12O40Template carries out being thermally treated resulting in object copper and tin sulphur engraved structure micro-
Rice ball.
Heat treatment temperature is 180 ~ 200 DEG C in step B, and processing time is 22 ~ 26h.
Sample solution is is transferred to polytetrafluoro container and is fixed in stainless steel cauldron by step B, by stainless steel reaction
Kettle is placed in baking oven and is heated.
Step B, which is further included, to be cooled down the copper and tin sulphur engraved structure micron ball, is cleaned.
The removal of impurities is to precipitate copper and tin sulphur engraved structure micron ball by centrifuging from ethylene glycol solution, and point
It is not washed alternately with deionized water and ethyl alcohol, washing times is more than twice.
The centrifugation is to centrifuge 8 ~ 12min under 5000 ~ 7000rpm.
Step B is further included is dried processing by the copper and tin sulphur engraved structure micron ball.
The drying process is vacuum drying, and drying temperature is 65 ~ 75 DEG C, and drying time is 5 ~ 7h.
The application of the present invention is application of the copper and tin sulphur engraved structure micron ball in photochemical catalyst is prepared.
The present invention is by polyanionic（Polyoxometallate POM）It is introduced into CTS systems and obtains engraved structure（It is porous）CTS
Micron ball, i.e. copper and tin sulphur mouth hollow structure micron ball, polyoxometallate is a kind of unique inorganic metal oxygen cluster, in addition to they are tied
It is the stabilization of structure, firm outer, the features such as extensive molecular dimension distribution, exclusive oxidation-reduction quality, Electronic Structure and acidity
So that more acid compounds have the property that many other compounds do not have, such as certain moduli plate and catalytic action.This
Outside, most of anionic surfaces have many negative electrical charge and unoccupied orbital, can receive additional electronic structure.Polyoxometallic acid
Salt plays the role of the formation of CTS porous structure micron balls as template very important.The shape of engraved structure CTS micron balls
It is as follows into mechanism：In the case of no addition polyoxometallate, hydrothermal system inner surface can higher these nanometer sheets progress
Rapid aggregation process, and only form small size layering CTS particles.Nucleus increases in system after polyoxometallate is added in, this
Sample one can, the crystallization time that extends particle, prevent nano particle rapid aggregation to reduce the surface of reaction system, therefore,
The diameter of the POM-CTS of synthesis is more relatively large than pure CTS particles, in addition, prolonged ultrasonic purification can lead to the hole of bigger
Diameter is formed.
Embodiment 1
By the SnCl of 2mM2.2H2O, the CuCl of 2mM2.2H2O, the thiocarbamide of 6mM and 10-3The K of mmol4SiW12O40It is added to
It dissolves, is transferred into the stainless steel autoclave of 100ml teflon lineds, and be maintained in the beaker of 50ml DMF
Heated in 200 DEG C of air oven for 24 hours, sediment centrifuges 10min from solution with 6000rpm, with deionized water and
Alternately washing 3 times of the ethyl alcohol of concentration of volume percent 10% obtain target after 6h dry under vacuum degree 0.1MPa, temperature 70 C
Object.
Embodiment 2
By the SnCl of 2mM2.2H2O, the CuCl of 2mM2.2H2O, the thiocarbamide of 2mM and 10-5The K of mmol4SiW12O40It is added to
It dissolves, is transferred into the stainless steel autoclave of 100ml teflon lineds, and be maintained in the beaker of 50ml DMF
Heated in 200 DEG C of air oven for 24 hours, sediment centrifuges 10min from solution with 6000rpm, with deionized water and
Alternately washing 3 times of the ethyl alcohol of concentration of volume percent 10% obtain target after 6h dry under vacuum degree 0.1MPa, temperature 70 C
Object.
Embodiment 3
By the SnCl of 2mM2.2H2O, the CuCl of 2mM2.2H2O, the thiocarbamide of 2mM and 10-4The K of mmol4SiW12O40It is added to
It dissolves, is transferred into the stainless steel autoclave of 100ml teflon lineds, and be maintained in the beaker of 50ml DMF
Heated in 200 DEG C of air oven for 24 hours, sediment centrifuges 10min from solution with 6000rpm, with deionized water and
Alternately washing 3 times of the ethyl alcohol of concentration of volume percent 10% obtain target after 6h dry under vacuum degree 0.1MPa, temperature 70 C
Object.
Embodiment 4
By the SnCl of 2mM2.2H2O, the CuCl of 2mM2.2H2O, the thiocarbamide of 2mM and 10-3The K of mmol4SiW12O40It is added to
It dissolves, is transferred into the stainless steel autoclave of 100ml teflon lineds, and be maintained in the beaker of 50ml DMF
Heated in 200 DEG C of air oven for 24 hours, sediment centrifuges 10min from solution with 6000rpm, with deionized water and
Alternately washing 3 times of the ethyl alcohol of concentration of volume percent 10% obtain target after 6h dry under vacuum degree 0.1MPa, temperature 70 C
Object.
Embodiment 5
By the SnCl of 2mM2.2H2O, the CuCl of 2mM2.2H2O, the K of the thiocarbamide of 2mM and 2mg4SiW12O40It is added to 50ml
It dissolves, is transferred into the stainless steel autoclave of 100ml teflon lineds in the beaker of DMF, and be maintained at 200 DEG C
It is heated in air oven for 24 hours, sediment centrifuges 10min from solution with 6000rpm, with deionized water and volume basis
Alternately washing 3 times of the ethyl alcohol of specific concentration 10% obtain object after 6h dry under vacuum degree 0.1MPa, temperature 70 C.
Embodiment 6
By the SnCl of 2mM2.2H2O, the CuCl of 2mM2.2H2O, the K of the thiocarbamide of 2mM and 2mg4SiW12O40It is added to 50ml
It dissolves, is transferred into the stainless steel autoclave of 100ml teflon lineds in the beaker of DMF, and be maintained at 200 DEG C
It is heated in air oven for 24 hours, sediment centrifuges 10min from solution with 6000rpm, with deionized water and volume basis
Alternately washing 3 times of the ethyl alcohol of specific concentration 10% obtain object after 6h dry under vacuum degree 0.1MPa, temperature 70 C.
The sulphur Cu-Sn-Zn engraved structure micron ball being prepared with embodiment 3 is tested：
The sulphur Cu-Sn-Zn engraved structure micron ball that embodiment 1 is prepared（That is CTS-POM）X-ray diffractogram of powder spectrum
See attached drawing 1, main characteristic diffraction peak appears in 28.72 °, and 32.79 °, 47.73 °, 56.33 °, 69.38 ° corresponding with 76.72 °
In CTS's（112）,（200）,（220）,（312）,（008）With（332）Face, this result meet kesterite crystal structures
CTS（Card No.: 26-0575）Although the stoichiometric ratio very little of POM in starting material, purer kesterite CTS
XRD diagram, the new signal of low angle is appeared in engraved structure micron ball CTS can be attributed to and engraved structure micron ball CTS
The relevant peaks of middle cocrystallization POM.In addition, the peak type of the compound very sharply shows synthesized engraved structure micron ball
The size of CTS particles is larger.The oxidation state of the CTS micron ball elements of synthesis is measured by high-resolution XPS analysis.After smooth
Copper, zinc, the XPS data of tin and sulphur are shown in Figure 2.Cu2p spectrum show two relatively narrow and symmetrical peaks of peak type, appear in
932eV is Cu2p3/2Energy area and 951.9 eV are Cu2p1/2Energy range in, this result and Cu2+Oxidation state be
Unanimously.Two feature 2p peaks of zinc are located at 1021.8 and 1044.8eV, can be split into 23eV, this shows the valence state of Zn-ef ficiency
It is 2+。Sn3d5/2Peak respectively appears in 486.8 and 495.2 eV, and split values show tin for 8.4 eV（IV）Oxidation state be 4+.It should
S2p3/2And 2p1/2The spectrum at peak is located at 162 and 168.1 eV respectively, and this is consistent with the sulphur in the CTS reported before.With it
It obtains that the situation that CTS particles observe is the same, and the template of introducing is tied altogether with CTS to a certain extent by template auxiliary synthesis
It is brilliant together, even as shown in figure 3, the signal of tungsten and element silicon is very faint, but still can be identified.Cause
This, with reference to XRD and XPS analysis as a result, we may safely draw the conclusion, embodiment 1 prepares obtained particle as novel CTS-
POM is semiconductor.
As shown in FIG. in attached drawing 2, synthesized CTS is the spheroidal particle of dispersion in the same size, and diameter is 10-15 μm
, the particle, which is deposited on, to be overlapped each other to form aggregate structure.It goes through it can be found that the spherome surface of micron ball is in more
Pore geometry configuration integrally seems similar with the structure of " crater ", this is to observe this kind of configuration in CTS materials for the first time.With
Compare, under identical reaction conditions, without SiW12In the case of（See Fig. 4）Flower-shaped CTS can only be accessed in system
Grain.Therefore, scanning electron microscope the result shows that, polyoxometallate plays the formation of CTS porous structure micron balls as template
Very important effect.Tem analysis to the morphological analysis of porous structure micron ball CTS as shown in figure 5, CTS-POM particles it is more
Permeability leads to different thickness distributions from surface to center, i.e. the more big corresponding depth in aperture is consequently increased.Therefore, according to
Above-mentioned experimental result, the possible formation mechenism of engraved structure CTS micron balls are as follows：In no situation for adding in polyoxometallate
Under, hydrothermal system inner surface can higher these nanometer sheets carry out rapid aggregation process, and only form small size layering CTS particles.
Nucleus increases in system after polyoxometallate is added in, and the surface for so reducing reaction system can, extend particle
Crystallization time, prevent nano particle rapid aggregation, so synthesis POM-CTS diameter it is more relatively large than pure CTS particles.I
Find simultaneously, prolonged ultrasonic purification can cause the aperture of bigger to be formed, therefore speculate the formation of POM-CTS spheres
In the process, the same density of the different orientations of growth and stability is not also just as and eventually leading to duct in separation and purification process
The generation of type defect.
Sample uv-visible absorption spectra prepared by embodiment 1 is shown in attached drawing 6.The result shows that compared to pure CTS particles institute
Synthesis CTS-POM particles show better optical absorption characteristics in visible region.The absorptivity for increasing light may be due to mixing
Enter heteropoly acid and the spectral response that heteropoly blue improves visible ray is formd under light excitation.
The light excitation of POM and CTS can both generate oxidation state or excitation state substance reacts with organic dyestuff or water.It grinds
The persons of studying carefully conduct in-depth research associated catalytic mechanism.In order to investigate the photocatalysis effect of POM-CTS, use herein
Rhodamine B (RhB) is as photocatalysis model.Light-catalyzed reaction carries out as follows：10 milligrams of powder is dispersed in the 10ppm of 50ml
RhB aqueous solutions and in the dark stir 60 minutes.Then irradiated by 300W xenon lamps, between liquid surface and lamp distance for 4 ~
5cm simultaneously continues to stir.Every 30 minutes, 3.0ml samples were taken out for analyzing.RhB（C/C0）To the relative concentration in reaction time
Shown in mapping（Attached drawing 7）, the degradation rate of pure CTS particles is relatively slow, there was only the degradation of 70% RhB after 4 hours, therewith
Higher degradation rate is shown compared to CTS-POM, the RhB degradations for having nearly 90% in the identical time.Photodegradation kinetics can be with table
It is shown as ln（C0/C）=kt, wherein k represent observed rate constant, the k values of POM-CTS be 0.025 this almost than pure CTS
(0.013) one times.In addition, adding in the RhB of equivalent to system again after reaction, test is repeated 3 POM-CTS's
Significant changes do not occur for photocatalytic activity.Circulation experiment shows that CTS-POM has good photocatalytic activity and stability.
As CTS-POM an important potential application we the experiment of photocatalytic hydrogen production by water decomposition has been carried out to it, and
With SiW12One compares during parallel test with kesterite types CTS is compared.It has main steps that with photocatalytic degradation RhB's
It is similar.Such as attached drawing 8（a）It is shown, individual SiW12Almost without H2Generation, shows individual SiW12It can hardly be excited by light.
In comparison, kesterite CTS show good hydrogen-producing speed, reach 39.7 μm of ol g-1h-1.When POM introduce CTS,
The CTS-POM of synthesis shows highest hydrogen evolution rate and production H is compared with pure CTS particles2Rate improves nearly 30%, reaches
（50.8μmol g-1h-1）, show that POM plays a key effect in photocatalysis.Meanwhile in order to study POM in light-catalyzed reaction
CTS material loads influence, experiment has carried out different loads and has compared, such as attached drawing 8（b）Shown, load capacity is catalyzed at 5%
Effect is best, further increases catalytic efficiency and can decrease instead.The stability of CTS-POM photocatalytic activities is ground
Study carefully.By the test of 12 hours, for the hydrogen generation efficiency of POM-CTS by three periodic linears without significant change, this shows CTS-
POM has stable photocatalytic activity.
It observes the phenomenon that such, not only shows there is the generation of synergistic effect between CTS and POM, also imply that POM rises
The key factor that photocatalysis hydrogen is promoted to generate.In addition, in view of the lumo energy of the reduction potential and CTS of polyoxometallate,
From CTS to SiW12LUMO electronics transfer be an incident exothermic process.After POM is integrated into CTS systems,
The electron transmission that CTS is generated by light excitation is to SiW12, this process can effectively improve the dissociation of the electron-hole pair of excitation
Efficiency simultaneously further improves photocatalysis performance, sees attached drawing 9.
We have successfully obtained CTS-POM micron balls by simple mild hydro-thermal method, and porous form is in CTS
It is seen for the first time in material.In photocatalysis experiment, CTS-POM shows photocatalytic activity more higher than pure CTS particles.This work
Point out polyoxometallate to the important function in CTS material structures guiding and photocatalytic process.In addition, we pass through more
Complete experimental data and further theory analysis propose the possible Crack cause of porous pattern and are urged with the light of CTS-POM
Change mechanism.
Claims (5)
1. a kind of preparation method of copper and tin sulphur engraved structure micron ball, it is characterised in that the copper and tin sulphur structure micron ball is a diameter of
10-15 μm, micron spherome surface is in porous geometric configuration, and aperture is 1 ~ 3nm, and hole depth is 1 ~ 3nm；The copper and tin sulphur engraved structure
The preparation method of micron ball includes the following steps：
A, by raw material copper chloride, stannous chloride, thiocarbamide and K4SiW12O40According to 1:1:3:10-3Molar ratio be dissolved in ethylene glycol
Middle formation sample solution；
B, sample solution is transferred to polytetrafluoro container and be fixed in stainless steel cauldron, stainless steel cauldron is placed in baking oven
It is heat-treated, heat treatment temperature is 180 ~ 200 DEG C, processing time is 22 ~ 26h, and it is micro- to obtain object copper and tin sulphur engraved structure
Rice ball.
2. preparation method according to claim 1, it is characterised in that step B includes carrying out copper and tin sulphur engraved structure micron ball
Cooling, removal of impurities.
3. preparation method according to claim 2, it is characterised in that the removal of impurities is that copper and tin sulphur engraved structure micron ball sinks
It forms sediment by centrifuging from ethylene glycol solution, and is alternately washed with deionized water and ethyl alcohol respectively, washing times two
More than secondary.
4. preparation method according to claim 1, it is characterised in that step B includes carrying out copper and tin sulphur engraved structure micron ball
It is dried.
5. preparation method according to claim 4, it is characterised in that described to be dried as vacuum drying, drying temperature 65
~ 75 DEG C, drying time is 5 ~ 7h.
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| 新型铜锡硫和铜锌锡硫材料的合成与光解水制氢性能研究;陈福昆;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20130715(第07期);第14页第1段、最后1段-第15页第1段以及第16页最后1段 * |
| 溶剂热体系中Keggin型多金属氧酸盐辅助合成氧化锌中空球结构及其性能的研究;李秋玉;《东北师范大学 博士学位论文》;20110215;第4.2.2节、第4.3.3节、第4.3.5节 * |
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