CN106192009B - One kind being used for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface and preparation method - Google Patents
One kind being used for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface and preparation method Download PDFInfo
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- CN106192009B CN106192009B CN201610631019.5A CN201610631019A CN106192009B CN 106192009 B CN106192009 B CN 106192009B CN 201610631019 A CN201610631019 A CN 201610631019A CN 106192009 B CN106192009 B CN 106192009B
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000004065 semiconductor Substances 0.000 title claims abstract description 27
- 238000005260 corrosion Methods 0.000 title claims abstract description 24
- 230000007797 corrosion Effects 0.000 title claims abstract description 21
- 125000000101 thioether group Chemical group 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052958 orpiment Inorganic materials 0.000 claims abstract description 8
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005642 Oleic acid Substances 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006104 solid solution Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 14
- 241000894006 Bacteria Species 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003708 ampul Substances 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000605178 Halothiobacillus neapolitanus Species 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KEWIUFDNNIFKJK-KVVVOXFISA-N (z)-octadec-9-enoic acid;hydrate Chemical compound O.CCCCCCCC\C=C/CCCCCCCC(O)=O KEWIUFDNNIFKJK-KVVVOXFISA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 244000007853 Sarothamnus scoparius Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ABSOMGPQFXJESQ-UHFFFAOYSA-M cesium;hydroxide;hydrate Chemical compound O.[OH-].[Cs+] ABSOMGPQFXJESQ-UHFFFAOYSA-M 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002362 energy-dispersive X-ray chemical map Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses one kind to be used for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface and preparation method.With alkali metal hydroxide (CsOHH2O), transition metal (Mn), binary solid solution (As2S3) and sulphur powder (S) be raw material, oleic acid and diethyl triamine are solvent, react 4-7 days in 130-160 DEG C of environment, obtain quaternary sulfide semiconductor material, chemical constitution formula are as follows: CsMnAsS3.The present invention has synthetic yield height, the advantages such as operating process is simple, and cost of material is low, and reaction condition is mild, and synthesis temperature is low.For the quaternary sulfide yield obtained using the present invention up to 90% or more, chemical purity is high, can be used for the fields such as anti-corrosion, antibacterial, battery, catalysis.
Description
Technical field
The invention belongs to inorganic semiconductor material fields, and in particular to one kind is used for the antibacterial corrosion-resistant quaternary of concrete surface
Sulfide semiconductor catalysis material and preparation method.
Background technique
Sulfide material is a kind of generally acknowledged defect semiconductor material, and this kind of compound according to the Nomenclature Composition and Structure of Complexes not
It together, can be many-sided with important purposes in light, electricity, magnetic etc..Transient metal sulfide then shows special photoelectric properties,
It is used in the fields such as electroluminescent, luminescence generated by light, sensor, phosphor and material of infrared window and photocatalysis extensive.
Ag8SnS6And CuInS2Equal ternary sulfides show good thermal stability, are good semiconductor materials, optical absorption exists
Visible light region has potential application.Simultaneously be used as new catalysts materials, will be widely used in catalysis, it is antibacterial,
The fields such as anti-corrosion.
Steel Bars in Concrete Structure, which is rusted, becomes a principal element for influencing armored concrete durability, all makes every year
At weight huge economic loss, solving corrosion of reinforcing steel bar is most pressing that current field of civil engineering scientific worker faces
One of business.Wherein, T- sulfur oxidizing bacterium, Thiobacillus X, to bite biology sulfuric acid corrosion caused by silicon bacterium be one of common concrete
Corrosion, detailed process are as follows: the organic and mineral suspensions in environment water are gradually deposited on coagulation with the flowing of water body
The surface of soil structure becomes attachment, and the sulfate ion in attachment is restored by sulphur reducing bacteria, generates hydrogen sulfide gas.Together
When, hydrogen sulfide gas is by complicated biochemical reaction, and oxidation generates acid stronger sulfuric acid, to reduce ambient enviroment
PH value.The hydrogen ion of sulfuric acid dissolution release is by diffusing into the inside of concrete, and the bar construction phase with inside concrete
Contact, so that the corrosion of concrete and reinforcing bar occur, seriously threatens the safety of concrete building structures.Semiconductor material can be with
As coating material, good bacteriostasis is played coated in concrete surface.It is excited since semiconductor energy is hard to bear to light
" light-catalyzed reaction " is carried out afterwards, chemical energy is generated, carries out redox reaction using the chemical energy of generation.Conductor photocatalysis
Basic principle be using semiconductor as catalysis material (or in conjunction with certain oxidant), in the light radiation of specific wavelength
Under, the extremely strong hole of oxidisability or reactive high hydroxyl radical free radical are generated in semiconductor surface.These oxidation activity ions
With organic pollutant, virus, bacterium be in contact with it is compound and generate strong destruction, cause organic pollutant to be dropped
Solution, virus is killed with bacterium, thus reach degradation environmental contaminants, restraining and sterilizing bacteria and corrosion-resistant purpose.
Currently, TiO2It is proved to be most widely used photochemical catalyst.But its bottleneck is, only in short wave ultraviolet light
Irradiation under Ti02Photocatalysis characteristic can be just shown, and ultraviolet light only accounts for the 3%~4% of sunlight, wherein can be by Ti02It absorbs
For the relatively low of light-catalyzed reaction.Therefore enhancing visible light absorption capacity substantially effectively utilizes solar energy resources, it has also become
The developing direction in one forward position of photochemical catalyst at present.Metal sulfide has very wide visible absorption range.Therefore, exploitation is new
Materials synthesis route, exploring and synthesizing new sulfide semiconductor system is one of the important channel to solve the above problems.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, and provide a kind of antibacterial for concrete surface
Corrosion-resistant quaternary sulfide semiconductor catalysis material and preparation method.Specific technical solution is as follows:
One kind being used for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface, and chemical constitution formula is
CsMnAsS3, belong to monoclinic system, P2 (1)/n space group, cell parameter α=90 °, β=95.675 (4) °, γ=90 °, Z=4,
Energy gap is 1.78eV.
The above-mentioned preparation method for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface, specifically
Are as follows: it with molar ratio is cesium hydroxide monohydrate, manganese metal, the binary solid solution of 1.0-2.0:1.0-2.0:0.5:2.0-3.5
Orpiment and elemental sulfur are raw material；Using volume ratio for 0.5-1.0:2.0-3.5 diethyl triamine and oleic acid as solvent；It will
Every 0.410-0.665 grams of raw material is added in solvent described in 2.5-4.5mL, reacts 4-7 days in 130-160 DEG C of baking oven, passes through
Quaternary sulfide semiconductor material C sMnAsS is obtained after deionized water and ethanol washing3。
The purposes of above-mentioned quaternary sulfide semiconductor material can be used as the antibacterial corrosion-resistant photocatalysis of concrete surface
Material, or it is used to prepare optical electro-chemistry semiconductor devices or solar battery buffer layer material.
Operation of the present invention process is simple and convenient, and cost of material is low, and reaction condition is mild etc., the quaternary prepared using this method
Sulfide semiconductor material, yield can reach 90% or more, and crystallite dimension reaches micron order or more, and chemical purity is higher.Half
The energy gap of conductor material is respectively 1.78eV, is had potential application in terms of conductor photocatalysis sterilization.
Detailed description of the invention
Fig. 1 is CsMnAsS3The shape appearance figure of crystal；
Fig. 2 is CsMnAsS3The EDX map of crystal shows the presence and its content of Cs, Mn, As and S element；
Fig. 3 is CsMnAsS3Structure chart；
Fig. 4 is according to CsMnAsS3The XRD spectrum and monocrystalline simulated diffraction figure that crystal obtains；
Fig. 5 is CsMnAsS3The visible diffusing reflection spectrum of solid-state UV；
Fig. 6 is CsMnAsS3When as antiseptic concrete coating material, corrosion potential-time of reinforcement in concrete is bent
Line.
Specific embodiment
The present invention is further elaborated and is illustrated with reference to the accompanying drawings and examples.Each embodiment in the present invention
Technical characteristic can carry out the corresponding combination under the premise of not conflicting with each other.
It is specifically disclosed in the present invention following a kind of for the antibacterial corrosion-resistant quaternary sulfide semiconductor light of concrete surface
Catalysis material CsMnAsS3, belong to monoclinic system, P2 (1)/n space group, cell parameterα=90 °, β=95.675 (4) °, γ=90 °,Z=4, energy gap 1.78eV.
CsMnAsS3The preparation method comprises the following steps: being the cesium hydroxide of 1.0-2.0:1.0-2.0:0.5:2.0-3.5 with molar ratio
Monohydrate, manganese metal, binary solid solution orpiment and elemental sulfur are raw material；It is 0.5-1.0:2.0-3.5 with volume ratio
Diethyl triamine and oleic acid be solvent；Solvent described in 2.5-4.5mL is added in every 0.410-0.665 grams of raw material in proportion
In, it is reacted 4-7 days in 130-160 DEG C of baking oven, quaternary sulfide semiconductor material is obtained after deionized water and ethanol washing
CsMnAsS3。
The binary solid solution orpiment can be used current material or prepare with the following method: be 2 by molar ratio:
3 As and S is packed into quartz ampoule and carries out tube sealing, then the quartz ampoule of sealing is put into Muffle furnace, is to slowly warm up to 680 DEG C, and protect
Temperature 12 hours, then cooled to room temperature open quartz ampoule block stock grind into powder is spare.Above-mentioned preparation parameter can root
It is adjusted according to test.
Embodiment 1
CsMnAsS3Crystal.Weigh initial feed CsOHH2O 1.5mmol(0.252g)、Mn 1.0mmol(0.055g)、
As2S30.5mmol (0.123g) and S 3.0mmol (0.096g) are put into water heating kettle, add diethyl triamine 0.5ml and oil
Water heating kettle is placed at 140 DEG C and reacts 5 days by sour 2.0mL.After reaction, water heating kettle is opened, product is taken out, respectively with distillation
Water and dehydrated alcohol wash 2 times, obtain red bulk crystals, yield 90%, 150-260 μm of crystallite dimension (see Fig. 1).Through list
Brilliant X-ray diffraction analysis, the crystal composition formula are CsMnAsS3, belong to monoclinic system, P2 (1)/n space group, cell parameterα=90 °, β=95.675 (4) °, γ=90 °,Z=4, crystal structure figure are as shown in Figure 3.EDX elemental analysis shows crystal tetra- kinds of members containing Cs, Mn, As, S
Element, and each element content ratio and single crystal diffraction analysis result are consistent (see Fig. 2).XRD powder diffraction peak and single crystal diffraction analyze mould
Quasi- map matches (see Fig. 4).It is 1.78eV that UV-vis map, which measures semiconductor material energy gap, (see Fig. 5).
In preparation process, each parameter can be adjusted slightly, and the fundamental performance parameter of product is essentially identical.It further provides for
Following two embodiments.
Embodiment 2
CsMnAsS3Crystal.Weigh initial feed CsOHH2O 2.0mmol(0.336g)、Mn 1.0mmol(0.055g)、
As2S30.5mmol (0.123g) and S 2.5mmol (0.080g) are put into water heating kettle, add diethyl triamine 1.0ml and oil
Water heating kettle is placed at 140 DEG C and reacts 5 days by sour 2.0mL.After reaction, water heating kettle is opened, product is taken out, respectively with distillation
Water and dehydrated alcohol wash 2 times, obtain orange bulk crystals, yield 30%.
Embodiment 3
CsMnAsS3Crystal.Weigh initial feed CsOHH2O 1.5mmol(0.252g)、Mn 2.0mmol(0.11g)、
As2S30.5mmol (0.123g) and S 3mmol (0.096g) are put into water heating kettle, add diethyl triamine 0.5ml and oleic acid
Water heating kettle is placed at 140 DEG C and reacts 6 days by 2.0mL.After reaction, water heating kettle is opened, product is taken out, uses distilled water respectively
It is washed 2 times with dehydrated alcohol, obtains orange bulk crystals, yield 50%.
Embodiment 4
With quaternary sulfide semiconductor material C sMnAsS obtained in embodiment 13, catalysis material is prepared, as coagulation
Native erosion shield, specific as follows:
Pretreatment: sand crosses 80 mesh screens, and concrete test block watering is wet.
It is dry-mixed: by 5 parts of CsMnAsS of weighing3, 20 parts of tricalcium aluminates, 45 parts of tricalcium silicates pour into container, are placed in batch mixer
In stir.
Wet mixing: being added 5 parts of water in the above-mentioned dry mixing material stirred evenly, is placed in batch mixer and is sufficiently mixed uniformly；It is mechanical
Stirring after ten minutes, is stirred on one side, and 15 parts and 10 parts water of load weighted sand are poured into blender again together on one side, continue to stir
10 minutes, eventually form finely dispersed coating.
It smears: picking the coating of above-mentioned preparation with rotary broom, be uniformly applied to the surface concrete test block (40*40*40mm).
Maintenance: test block is statically placed in normal temperature air coagulation forming after 5 days.
Corrosion test: will not smear anti-corrosion material (number UC-01) and smear CsMnAsS3(number C-02) test block is simultaneously
It is put into seal cup, and injects the sewage that 400ml has bacterium (T- sulfur oxidizing bacterium, bites silicon bacterium at Thiobacillus X), daylight light irradiation
After 10 days, test block is then taken out, is tested with electrochemical workstation, Evaluation of Corrosion Resistance is carried out.Test result such as Fig. 6, not
Smear CsMnAsS3The corrosion potential of the reinforcement in concrete of (number UC-01) is lower than smearing CsMnAsS3(number C-02's) is mixed
The corrosion potential of reinforcing bar, illustrates CsMnAsS in solidifying soil3Reinforcement in concrete corrosion can be substantially reduced as anticorrosion coating material
Speed.
Above-mentioned embodiment is only a preferred solution of the present invention, so it is not intended to limiting the invention, all
The mode of equivalent substitution or equivalent transformation technical solution obtained is taken, is fallen within the scope of protection of the present invention.
Claims (1)
1. a kind of preparation method for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface, feature
It is, the quaternary sulfide semiconductor catalysis material chemical constitution formula is CsMnAsS3, belong to monoclinic system, P2 (1)/
N space group, cell parameter a=10.1851 (5), b=6.4854 (3), c=10.3638 (5), α=90 °, β=95.675 (4) °,
γ=90 °, V=681.22 (8)3, Z=4, energy gap is 1.78 eV；It is described the preparation method is as follows: weighing initial feed CsOH
H2O 1.5 mmol、Mn 1.0 mmol、As2S30.5 mmol and 3.0 mmol of S are put into water heating kettle, add diethyl three
Water heating kettle is placed at 140 DEG C and reacts 5 days by 2.0 mL of amine 0.5ml and oleic acid；After reaction, water heating kettle is opened, takes out and produces
Object is washed 2 times with distilled water and dehydrated alcohol respectively, obtains quaternary sulfide semiconductor material C sMnAsS3。
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