CN106423215A - 一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 - Google Patents
一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 Download PDFInfo
- Publication number
- CN106423215A CN106423215A CN201610630963.9A CN201610630963A CN106423215A CN 106423215 A CN106423215 A CN 106423215A CN 201610630963 A CN201610630963 A CN 201610630963A CN 106423215 A CN106423215 A CN 106423215A
- Authority
- CN
- China
- Prior art keywords
- quaternary sulfide
- sulfide semiconductor
- quaternary
- csmnas
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000004065 semiconductor Substances 0.000 title claims abstract description 32
- 125000000101 thioether group Chemical group 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 11
- 230000003385 bacteriostatic effect Effects 0.000 title abstract 2
- 239000003755 preservative agent Substances 0.000 title abstract 2
- 230000002335 preservative effect Effects 0.000 title abstract 2
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005642 Oleic acid Substances 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000006104 solid solution Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005260 corrosion Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000007797 corrosion Effects 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 17
- 230000000844 anti-bacterial effect Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 229910052958 orpiment Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000005622 photoelectricity Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- -1 alkali metal hydroxide compound Chemical class 0.000 abstract 1
- 238000005536 corrosion prevention Methods 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
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 241000605178 Halothiobacillus neapolitanus Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002829 reductive 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
- 238000001228 spectrum Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-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
- 230000004913 activation Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229940007424 antimony trisulfide Drugs 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 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
- 238000004140 cleaning Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 238000004332 deodorization 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
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001151 other effect Effects 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
- 230000005855 radiation Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000010959 steel Substances 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
- 238000004065 wastewater treatment Methods 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
- B01J27/02—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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5035—Silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
- C04B41/68—Silicic acid; Silicates
-
- 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
-
- 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
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
- C04B2103/69—Fungicides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/26—Corrosion of reinforcement resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Structural Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途。以碱金属氢氧化合物(CsOH·H2O)、过渡金属(Mn)、二元固溶体(As2S3)和硫粉(S)为原料，油酸和水合肼为溶剂，在130‑160℃环境中反应4‑7天，得到四元硫化物半导体材料，化学组成式为：CsMnAs3S6。本发明具有合成产率高，操作过程简单，原料简单且成本低，反应条件温和，合成温度低等优点。采用本发明得到的四元硫化物产率达90％以上，化学纯度高，可用于防腐、抑菌、电池、催化等领域。
Description
技术领域
本发明属于无机半导体材料领域，具体涉及一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途。
背景技术
半导体光催化材料以其在光致电、空气净化、杀菌除臭、废水处理等领域具有的独特功能而备受研究者关注。光催化技术是从20世纪70年代逐步发展起来的一门新兴环保技术，它是根据半导体材料在光照条件下材料表面能受激活化的特性，达到氧化分解有机物、还原重金属离子、杀灭细菌和消除异味等效果。半导体光催化技术作为一种环保的新技术，在降解污染物方面具有诸多优点，如：降解没有选择性，不会产生二次污染；可以降低能量和原材料的消耗；光催化剂具有廉价、无毒、稳定，以及可以重复利用等特点。因此，该技术在抗菌、防腐、净化空气、改善水质及优化环境等方面会产生巨大的社会效益和经济效益，以具有广阔的应用前景。硫化物材料是一类公认的优良半导体材料，且这类化合物根据组成和结构的不同，可以在光、电、磁等多方面具有重要的用途。过渡金属硫化物则表现出特异的光电性能，在电致发光、光致发光、传感器、磷光体和红外窗口材料以及光催化等领域使用广泛。ZnIn2S4和CuInS2等三元硫化物显示出良好的光催化活性，是良好半导体材料，其光学吸收在可见光区域具有潜在的应用价值。同时作为新型催化剂材料，将广泛地应用在催化、抑菌、防腐等领域。
半导体光催化的基本原理是利用半导体作为光催化材料(或与某种氧化剂结合)，在特定波长的光辐射下，在半导体表面产生氧化性极强的空穴或反应性极高的羟基自由基。这些氧化活性离子与有机污染物、病毒、细菌发生接触和复合而产生强烈的破坏作用，导致有机污染物被降解，病毒与细菌被杀灭，从而达到降解环境污染物，抑菌杀菌和防腐的目的。
混凝土结构中钢筋被锈蚀成为影响钢筋混凝土耐久性的一项主要因素，每年都造成重大的经济损失，解决钢筋腐蚀问题是当前土木工程领域科技工作者面临的最紧迫的任务之一。其中，T-硫氧化菌、硫杆菌X、噬硅菌造成的生物硫酸腐蚀是其中一种常见的混凝土腐蚀，半导体材料可以作为表面涂层材料，涂覆在混凝土表面起到很好的抑菌作用。
目前，TiO2被证明是应用最广泛的光催化剂。但是其瓶颈在于，只有在短波紫外光的照射下Ti02才能表现出光催化特性，而紫外光仅占太阳光的3％～4％，其中能被Ti02吸收用于光催化反应的紫外光更低。因此增强可见光吸收能力，充分有效地利用太阳能资源，已成为目前光催化剂一个前沿的发展方向。金属硫化物具有很宽的可见光吸收范围。因此，开发新的材料合成路线，探索合成新的硫化物半导体体系是解决上述问题的重要途径之一。
发明内容
本发明的目的在于克服现有技术中存在的不足，并提供一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料制备方法。具体技术方案如下：
一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料，其化学组成式为CsMnAs3S6，属于三方晶系，R-3空间群，晶胞参数 α＝90°，β＝90°，γ＝120°，Z＝3，能隙为2.08eV。
上述用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料的制备方法，以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.5的氢氧化铯一水合物、金属锰、二元固溶体三硫化二砷和单质硫为原料；以体积比为0.5-1.0：2.0-3.5的85％水合肼和油酸为溶剂；将每0.410-0.665克的原料加入2.5-4.5mL所述的溶剂中，在130-160℃环境中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料CsMnAs3S6。
上述四元硫化物半导体材料的用途，可以作为用于临海混凝土结构抑菌防腐的混凝土防腐光催化材料，或用于制备光电化学半导体器件或太阳能电池过渡层材料。
本发明操作过程简单方便，原料成本低，反应条件温和等，采用本方法制备的四元硫化物半导体材料，产率可达到90％以上，晶粒尺寸达到微米级以上，且化学纯度较高。半导体材料的能隙分别为2.08eV，在半导体光催化杀菌方面具有潜在的应用价值。
附图说明
图1为CsMnAs3S6晶体的形貌图；
图2为CsMnAs3S6晶体的EDX图谱，表明了Cs、Mn、As和S元素的存在及其含量；
图3为CsMnAs3S6的结构图；
图4为根据CsMnAs3S6晶体得到的XRD图谱与单晶模拟衍射图；
图5为CsMnAs3S6的固态紫外可见漫反射光谱；
图6为CsMnAs3S6作为混凝土防腐涂层材料时，混凝土中钢筋的腐蚀电位-时间曲线。
具体实施方式
下面结合附图和实施例对本发明做进一步阐述和说明。本发明中各个实施方式的技术特征在没有相互冲突的前提下，均可进行相应组合。
本发明中具体公开了以下一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料CsMnAs3S6，属于三方晶系，R-3空间群，晶胞参数α＝90°，β＝90°，γ＝120°，Z＝3，能隙为2.08eV。
CsMnAs3S6的制备方法为：以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.5的氢氧化铯一水合物、金属锰、二元固溶体三硫化二砷和单质硫为原料；以体积比为0.5-1.0：2.0-3.5的85％水合肼和油酸为溶剂；按比例将每0.410-0.665克的原料加入2.5-4.5mL所述的溶剂中，在130-160℃烘箱中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料CsMnAs3S6。
本发明下述实施例中二元固溶体三硫化二砷可采用现有材料或用如下方法制备：将摩尔比为2:3的As和S装入石英管进行封管，再把密封的石英管放入马弗炉中，缓慢升温至680℃，并保温12小时，再自然冷却至室温，打开石英管将块状原料研磨成粉末备用。制备过程中的参数可以根据需要进行调整。当然二元固溶体硫化锑也可采用市售的现有材料。
实施例1
CsMnAs3S6晶体。称取初始原料CsOH·H2O 1.5mmol(0.252g)、Mn 1.0mmol(0.055g)、As2S3 0.5mmol(0.123g)和S 3.0mmol(0.096g)放入水热釜中，再加入85％水合肼0.5ml和油酸2.0mL，将水热釜置于140℃下反应5天。反应结束后，打开水热釜，取出产物，分别用蒸馏水和无水乙醇洗涤2次，得到橘色块状晶体，产率为90％，晶粒尺寸150-300μm(见图1)。经单晶X射线衍射分析，该晶体组成式为CsMnAs3S6，，R-3空间群，晶胞参数 α＝90°，β＝90°，γ＝120°，Z＝3，晶体结构图如图3所示。EDX元素分析表明晶体含Cs、Mn、As、S四种元素，且各元素含量比与单晶衍射分析结果一致(见图2)。XRD粉末衍射峰与单晶衍射分析模拟图谱相吻合(见图4)。UV-vis图谱测得半导体材料能隙为2.08eV(见图5)。
制备过程中，各参数可以略作调整，其产品的基本性能参数基本相同。进一步提供下述两个实施例。
实施例2
CsMnAs3S6晶体。称取初始原料CsOH·H2O 2.0mmol(0.336g)、Mn 1.0mmol(0.055g)、As2S3 0.5mmol(0.123g)和S 2.5mmol(0.080g)放入水热釜中，再加入水合肼0.5ml和油酸2.0mL，将水热釜置于140℃下反应5天。反应结束后，打开水热釜，取出产物，分别用蒸馏水和无水乙醇洗涤2次，得到橘色块状晶体，产率为20％。
实施例3
CsMnAs3S6晶体。称取初始原料CsOH·H2O 1.5mmol(0.252g)、Mn 2.0mmol(0.11g)、As2S3 0.5mmol(0.123g)和S 3mmol(0.096g)放入水热釜中，再加入水合肼0.5ml和油酸2.0mL，将水热釜置于140℃下反应6天。反应结束后，打开水热釜，取出产物，分别用蒸馏水和无水乙醇洗涤2次，得到橘色块状晶体，产率为70％。
实施例4
以实施例1中所得的四元硫化物半导体材料CsMnAs3S6，制备光催化材料，作为混凝土防腐蚀涂层，具体如下：
预处理：砂过80目筛网，混凝土试块洒水湿润。
干混：将称量的5份CsMnAs3S6，20份铝酸三钙，45份硅酸三钙倒入容器，置于混料机中充分搅拌均匀。
湿混：在上述搅拌均匀的干拌料中加入水5份，置于混料机中充分混合均匀；机械搅拌10分钟后，一边搅拌，一边再把称量好的砂15份和10份水一起倒入搅拌机中，继续搅拌10分钟，最后形成分散均匀的涂料。
涂抹：用滚筒刷沾取上述制备的涂料，均匀涂抹于混凝土试块(40*40*40mm)表面。
养护：试块静置于常温空气中5天后凝固成型。
腐蚀测试：将未涂抹防腐材料(编号UC-01)和涂抹CsMnAs3S6(编号C-01)试块同时放入密封杯中，并注入400ml带有细菌(T-硫氧化菌、硫杆菌X、噬硅菌)的污水，日光灯照射10天后，然后取出试块，用电化学工作站进行测试，进行腐蚀性能评价。测试结果如图6,涂抹CsMnAs3S6(编号C-01)的混凝土中钢筋的腐蚀电位高于未涂抹CsMnAs3S6(编号UC-01)的混凝土中钢筋的腐蚀电位，说明CsMnAs3S6作为防腐涂层材料可以明显降低混凝土中钢筋腐蚀的速度。
以上所述的实施例只是本发明的一种较佳的方案，然其并非用以限制本发明，凡采取等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。
Claims (4)
1.一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料，其特征在于，其化学组成式为CsMnAs3S6，属于三方晶系，R-3空间群，晶胞参数 α＝90°，β＝90°，γ＝120°，Z＝3，能隙为2.08eV。
2.一种如权利要求1所述的用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料的制备方法，其特征在于以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.5的氢氧化铯一水合物、金属锰、二元固溶体三硫化二砷和单质硫为原料；以体积比为0.5-1.0：2.0-3.5的85％水合肼和油酸为溶剂；将每0.410-0.665克的原料加入2.5-4.5mL所述的溶剂中，在130-160℃环境中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料CsMnAs3S6。
3.一种如权利要求1所述的用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料的用途，其特征在于，作为混凝土防腐光催化材料。
4.一种如权利要求1所述的四元硫化物半导体材料的用途，其特征在于，用于制备光电化学半导体器件或太阳能电池过渡层材料。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610630963.9A CN106423215B (zh) | 2016-08-03 | 2016-08-03 | 一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610630963.9A CN106423215B (zh) | 2016-08-03 | 2016-08-03 | 一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106423215A true CN106423215A (zh) | 2017-02-22 |
| CN106423215B CN106423215B (zh) | 2019-02-22 |
Family
ID=58185002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610630963.9A Expired - Fee Related CN106423215B (zh) | 2016-08-03 | 2016-08-03 | 一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423215B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790241B (zh) * | 2019-05-22 | 2021-04-20 | 内蒙古师范大学 | 一种硫属化合物及其制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862782A (zh) * | 2015-03-31 | 2015-08-26 | 浙江大学 | 一种四元硫化物半导体材料及其制备方法和用途 |
| CN105016385A (zh) * | 2014-04-21 | 2015-11-04 | 中国科学院上海硅酸盐研究所 | 层状多元光电硫化物的水热制备方法 |
| CN105236482A (zh) * | 2015-09-02 | 2016-01-13 | 浙江大学 | 一种四元硫锑化合物ACuSb2S4半导体材料 |
| CN105481010A (zh) * | 2015-11-26 | 2016-04-13 | 浙江大学 | 一种高产率四元硫属化合物半导体材料及其制备方法和用途 |
| CN105525354A (zh) * | 2016-01-29 | 2016-04-27 | 浙江大学 | 一种四元硫代砷酸盐化合物半导体材料及其制备方法和用途 |
| CN105696080A (zh) * | 2016-01-29 | 2016-06-22 | 浙江大学 | 一种四元硫属化合物半导体材料及其制备方法和用途 |
-
2016
- 2016-08-03 CN CN201610630963.9A patent/CN106423215B/zh not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016385A (zh) * | 2014-04-21 | 2015-11-04 | 中国科学院上海硅酸盐研究所 | 层状多元光电硫化物的水热制备方法 |
| CN104862782A (zh) * | 2015-03-31 | 2015-08-26 | 浙江大学 | 一种四元硫化物半导体材料及其制备方法和用途 |
| CN105236482A (zh) * | 2015-09-02 | 2016-01-13 | 浙江大学 | 一种四元硫锑化合物ACuSb2S4半导体材料 |
| CN105481010A (zh) * | 2015-11-26 | 2016-04-13 | 浙江大学 | 一种高产率四元硫属化合物半导体材料及其制备方法和用途 |
| CN105525354A (zh) * | 2016-01-29 | 2016-04-27 | 浙江大学 | 一种四元硫代砷酸盐化合物半导体材料及其制备方法和用途 |
| CN105696080A (zh) * | 2016-01-29 | 2016-06-22 | 浙江大学 | 一种四元硫属化合物半导体材料及其制备方法和用途 |
Non-Patent Citations (2)
| Title |
|---|
| RATNASABAPATHY G. LYER ET AL.: ""[Mn2(AsS4)4]8-and [Cd2(AsS4)2(AsS5)2]8-: Discrete Clusters with High Negative Charge from Alkali Metal Polythioarsenate Fluxes"", 《INORGANIC CHEMISTRY》 * |
| 候艳巧等: ""层状硫化物K2xMnxSn3-xS6与Th(IV)的离子交换性能研究"", 《稀有金属》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106423215B (zh) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104174408B (zh) | 一种具有可见光响应的铬铁钒酸盐光催化材料及其制备方法和应用 | |
| CN103623847B (zh) | 一种CdSe-Bi2WO6光催化剂的制备方法 | |
| CN106944074B (zh) | 一种可见光响应型复合光催化剂及其制备方法和应用 | |
| CN107376943A (zh) | 一种铌酸钙钾/硫化镉复合材料的制备方法与用途 | |
| Liu et al. | A novel Z-scheme BiPO4-Bi2O2 (OH)(NO3) heterojunction structured hybrid for synergistic photocatalysis | |
| CN107511154A (zh) | 一种海胆状CeO2/Bi2S3复合可见光催化剂及其制备方法 | |
| Pascariu et al. | Surface morphology effects on photocatalytic activity of metal oxides nanostructured materials immobilized onto substrates | |
| Zhang et al. | Photocatalytic removal organic matter and bacteria simultaneously from real WWTP effluent with power generation concomitantly: Using an ErAlZnO photo-anode | |
| Zhao et al. | Polyoxometalates-doped TiO 2/Ag hybrid heterojunction: removal of multiple pollutants and mechanism investigation | |
| Fang et al. | Cuprous oxide/titanium dioxide composite photocatalytic decolorization of reactive brilliant red X-3B dyes wastewater under visible light | |
| CN103785422B (zh) | 菜花状CdS纳米微球光催化剂的制备方法及其应用 | |
| CN1327953C (zh) | 硒化镉改性的纳米氧化钛光催化剂及制备方法 | |
| Fang et al. | Optical and photocatalytic properties of Er 3+ and/or Yb 3+ doped TiO 2 photocatalysts | |
| CN106732535A (zh) | 一种光催化剂Bi2Mo3O12及其制备方法 | |
| CN106423215A (zh) | 一种用于临海混凝土结构抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 | |
| CN110180557B (zh) | 一种Ag2S/TiO2复合光催化剂的制备方法及其应用 | |
| Topcu Sendogdular | TiO2/BiVO4 nanofibers: visible light-driven photocatalysts for indigo dye remediation | |
| Rahaman et al. | Nanoarchitectonics earth-abundant chalcogenide Cu 2 SnS 3 thin film using ultrasonic spray pyrolysis for visible light-driven photocatalysis | |
| CN108554427A (zh) | 一种In2O3/BiOI半导体复合光催化剂及其制备方法和用途 | |
| CN112642447B (zh) | 一种近红外光响应的Ag2S-Bi4NbO8Cl复合光催化剂的制备方法 | |
| Lu et al. | NGO/ZnO2/ZnO heterojunctions with self-accelerating photocatalysis for efficient degradation of organic dyes | |
| CN106268867B (zh) | 一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 | |
| CN106192009B (zh) | 一种用于混凝土表面抑菌防腐的四元硫化物半导体光催化材料及制备方法 | |
| CN106082327B (zh) | 一种用于混凝土防腐的四元硫化物半导体材料及制备方法 | |
| CN106345492A (zh) | 一种用于海洋工程混凝土结构杀菌防腐的四元硫化物半导体光催化材料及制备方法和用途 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190222 |