CN110252423A - A kind of organically-modified MoCdS3Composite material and its synthetic method and application - Google Patents
A kind of organically-modified MoCdS3Composite material and its synthetic method and application Download PDFInfo
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- CN110252423A CN110252423A CN201910640952.2A CN201910640952A CN110252423A CN 110252423 A CN110252423 A CN 110252423A CN 201910640952 A CN201910640952 A CN 201910640952A CN 110252423 A CN110252423 A CN 110252423A
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- mocds
- composite material
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- electronegative
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- 239000000463 material Substances 0.000 title abstract description 28
- 238000010189 synthetic method Methods 0.000 title abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 120
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 54
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 28
- 150000001661 cadmium Chemical class 0.000 claims abstract description 14
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010865 sewage Substances 0.000 claims abstract description 5
- -1 thio ammonium molybdate Chemical compound 0.000 claims description 62
- 239000011609 ammonium molybdate Substances 0.000 claims description 56
- 229940010552 ammonium molybdate Drugs 0.000 claims description 56
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 56
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 55
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 40
- 238000003786 synthesis reaction Methods 0.000 claims description 39
- 230000015572 biosynthetic process Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000006228 supernatant Substances 0.000 claims description 28
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 27
- 229940113088 dimethylacetamide Drugs 0.000 claims description 27
- 239000013049 sediment Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract description 44
- 238000006731 degradation reaction Methods 0.000 abstract description 28
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 26
- 230000015556 catabolic process Effects 0.000 abstract description 24
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 16
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005286 illumination Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 239000012044 organic layer Substances 0.000 abstract description 2
- 230000002688 persistence Effects 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 58
- 239000006185 dispersion Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 31
- 229940106691 bisphenol a Drugs 0.000 description 29
- 239000007864 aqueous solution Substances 0.000 description 27
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 22
- 229940012189 methyl orange Drugs 0.000 description 22
- 229910052961 molybdenite Inorganic materials 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 15
- 238000005119 centrifugation Methods 0.000 description 14
- 238000007710 freezing Methods 0.000 description 13
- 230000008014 freezing Effects 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910003472 fullerene Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XQQSWXUDAPLMKD-UHFFFAOYSA-N N,N-dimethylheptadecan-1-amine hydrobromide Chemical compound Br.CCCCCCCCCCCCCCCCCN(C)C XQQSWXUDAPLMKD-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HEZBNJBUCQQDFI-UHFFFAOYSA-N [N]=O.CC1=C(NC=C1)C Chemical class [N]=O.CC1=C(NC=C1)C HEZBNJBUCQQDFI-UHFFFAOYSA-N 0.000 description 1
- BKCQZEKBKFFBQB-UHFFFAOYSA-N [S-2].[Cd+2].[Mo](=S)=S Chemical compound [S-2].[Cd+2].[Mo](=S)=S BKCQZEKBKFFBQB-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 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 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002211 ultraviolet spectrum 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B01J35/33—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/02—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
Abstract
The present invention discloses a kind of organically-modified MoCdS3Composite material and its synthetic method and application belong to persistence organic pollutant degradation field.The present invention uses Thiomolybdate and cadmium salt, and one step hydro thermal method synthesizes to obtain electronegative MoCdS3Composite material；Then using cetyl trimethylammonium bromide to obtained electronegative MoCdS3Composite material progress is organically-modified, obtains organically-modified MoCdS3Composite material.The organically-modified MoCdS3Presence of the composite material due to cadmium sulfide and molybdenum disulfide composite heterogenous junction and cetyl trimethylammonium bromide organic layer, it can be realized the fast degradation under visible light illumination condition to BPA and MO, and the material also has the advantages that synthetic method is simple, anti-light corrosive power is strong, stability is high, reusable rate is high, suitable in the sewage treatment containing BPA/MO.
Description
Technical field
The invention belongs to persistence organic pollutant degradation fields, more specifically to a kind of organically-modified MoCdS3
Composite material and its synthetic method and application.
Background technique
Currently, with increasingly severe energy crisis and constantly break out environmental pollution the problems such as, solar energy is recognized
Utilization for the new energy for being most sufficient, most green environmental protection, solar energy is receive more and more attention and studies.Partly lead
Body catalysis material due to its synthetic method is simple, low in cost, redox ability is strong, redox does not have selectivity,
(Sakthivel, S. are widely studied and used to the features such as stability is high, environmentally protective；Neppolian,B.；Shankar,
M.V.；Arabindoo,B.；Palanichamy,M.；Murugesan,V.,Solar photocatalytic
degradation of azo dye:comparison of photocatalytic efficiency of ZnO and
TiO2.Solar Energy Materials and Solar Cells 2003,77,(1),65-82；Roy,S.C.；
Varghese,O.K.；Paulose,M.；Grimes,C.A.,Toward Solar Fuels:Photocatalytic
Conversion of Carbon Dioxide to Hydrocarbons.Acs Nano 2010,4,(3),1259-1278)。
Moreover, a variety of semiconductor materials are by substep synthesis system in order to improve the light utilization efficiency of semiconductor material and catalytic efficiency
At composite semiconductor hetero-junctions receive more and more attention and study.
Up to the present, there is a large amount of photochemical catalyst is studied to be used to remove some special pollutants, curing
Molybdenum and cadmium sulfide are two kinds of (Iwashina, K. therein；Iwase,A.；Ng,Y.H.；Amal,R.；Kudo,A.,Z-
Schematic Water Splitting into H2and O2Using Metal Sulfide as a Hydrogen-
Evolving Photocatalyst and Reduced Graphene Oxide as a Solid-State Electron
Mediator.Journal of the American Chemical Society 2015,137,(2),604-607；Zhao,
W.；Liu,Y.；Wei,Z.；Yang,S.；He,H.；Sun,C.,Fabrication of a novel p–n
heterojunction photocatalyst n-BiVO 4@p-MoS 2 with core–shell structure and
its excellent visible-light photocatalytic reduction and oxidation
activities.Applied Catalysis B:Environmental 2016,185,242-252).Cadmium sulfide is due to its taboo
With narrow, it is seen that light abstraction width is wide, it is considered to be a kind of visible photosemiconductor catalysis material well.Molybdenum disulfide is due to its class
The features such as layer structure of graphene, stability is high, almost fully absorbs in visible-range, and conductive capability is strong is also extensive
Research.Cadmium sulfide and molybdenum disulfide semiconductor composite Photocatalyzed Hydrogen Production and in terms of achieve it is very big
Progress (Ho, W.K.；Yu,J.C.；Lin,J.；Yu,J.G.；Li,P.S.,Preparation and photocatalytic
behavior of MoS2 and WS2 nanocluster sensitized TiO2.Langmuir 2004,20,(14),
5865-5869；Lin,J.；Li,B.；He,Y.；Pantelides,S.T.；Zhou,W.；Vajtai,R.；Ajayan,P.M.,
Defects Engineered Monolayer MoS2 for Improved Hydrogen Evolution
Reaction.Nano letters 2016,16,(2),1097-103)。
It is found through retrieval, Chinese Patent Application No. 201610076935.7, the applying date on 2 3rd, 2016 patents of invention
Application disclose a kind of molybdenum disulfide-cadmium sulfide nano composite material and preparation method thereof in photocatalysis Decomposition aquatic products hydrogen
Using preparation method includes preparing Nano cadmium sulphide first with solvent-thermal method；It is former on the Nano cadmium sulphide with hydro-thermal method again
Position growth stratiform nano-sulfur molybdenum, the invention in stratiform and are unformed knot using the molybdenum disulfide on Nano cadmium sulphide surface
Structure, as photocatalysis Decomposition aquatic products hydrogen catalyst in use, a large amount of work can be provided for atomic reaction of hydrogen in photoelectron and water
Property site, improve catalytic activity.
In addition, Chinese Patent Application No. 201810366049.7, the application for a patent for invention in April 23 2018 applying date is public
A kind of CdS/MoS is opened2/C60C(COOH)2The preparation and its application of trielement composite material, preparation method include first using letter
Single solvent-thermal method prepares CdS and MoS respectively2Nano material, then surface both is bound to each other to form CdS/MoS2Binary is multiple
Condensation material, finally by itself and prepared C60Carboxylic acid derivates C60C(COOH)2Adsorb it is compound, prepare containing difference
C60C(COOH)2The trielement composite material of load capacity；C60C(COOH)2Preparation method be included under conditions of anhydrous and oxygen-free, will
Fullerene is dissolved in new steaming toluene, bromo diethyl malonate and 1 is added, 11 carbon -7- alkene of 8- diazabicylo is stirred to react
Fullerene diethyl malonate is first prepared afterwards, then resulting product fullerene diethyl malonate is dissolved in toluene, and hydrogen is added
Change sodium to be heated to reflux to obtain fullerene malonate derivative, finally by C60C(COOH)2It is dissolved in toluene, is configured to a certain concentration
C60C(COOH)2Toluene solution.The invention utilizes C60As host material and above-mentioned semiconductor nano material (CdS/MoS2Two
First composite material) carry out it is compound, pass through C60The big π structure of conjugation and property feature of itself promote the transfer of light induced electron, from
And the recombination rate of light induced electron and hole in photocatalytic process can be effectively reduced, the activity of conductor photocatalysis is improved, is had
Effect improves CdS/MoS2Under visible light to the degradation speed of rhodamine B.But CdS/MoS in the invention2/C60C(COOH)2Ternary
The synthetic method complexity of composite material, at high cost, C60C(COOH)2It is not easy to prepare and utilizes C60C(COOH)2The big π structure of conjugation
The ability for improving conductor photocatalysis activity and degradation efficiency is limited, therefore it is high urgently to develop a kind of low energy consumption, degradation efficiency
Semiconductor catalysis material.
Summary of the invention
1. to solve the problems, such as
For semiconductor catalysis material in the prior art preparation method is complicated, light utilization efficiency and degradation efficiency need into
The problem of one step improves, the present invention provides a kind of organically-modified MoCdS3Composite material and its synthetic method and application.This hair
Bright to use Thiomolybdate and cadmium salt, one step hydro thermal method synthesizes to obtain electronegative MoCdS3Composite material then uses 16
Alkyl trimethyl ammonium bromide is to obtained electronegative MoCdS3Composite material progress is organically-modified, obtains organically-modified MoCdS3
Composite material.The organically-modified MoCdS3Composite material can extend light due to forming cadmium sulfide and molybdenum disulfide composite heterogenous junction
The service life of raw electrons and holes, and since cetyl trimethylammonium bromide is modified, enhance the absorption to BPA/MO, improves
The contact probability of BPA/MO and composite material realize the fast degradation to BPA/MO to improve light utilization efficiency and degradation efficiency.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
The organically-modified MoCdS of a kind of synthesis of the invention3The method of composite material, comprising the following steps:
S1, using Thiomolybdate and cadmium salt, one step hydro thermal method synthesizes to obtain electronegative MoCdS3Composite material；
S2, using cetyl trimethylammonium bromide to electronegative MoCdS obtained in step S13Composite material carries out
It is organically-modified, obtain organically-modified MoCdS3Composite material.
Preferably, the Thiomolybdate in the step S1 is four thio ammonium molybdate, and cadmium salt is cadmium nitrate, wherein tetrathio
The mass ratio of ammonium molybdate and cadmium nitrate is 1.5~2.0.
Preferably, the electronegative MoCdS in the step S23The matter of composite material and cetyl trimethylammonium bromide
Amount is than being 3.0~4.0.
Preferably, the specific steps of the step S1 are as follows:
(1) Thiomolybdate and cadmium salt are dissolved in dimethyl acetamide, stirring obtains thio molybdic acid up to being completely dissolved
The mixed liquor of salt and cadmium salt；
(2) mixed liquor of Thiomolybdate obtained in step (1) and cadmium salt is moved in hydrothermal reaction kettle, hydrothermal synthesis
Obtain electronegative MoCdS3Composite material precipitating；
(3) electronegative MoCdS obtained in collection step (2)3Composite material precipitating, and with dehydrated alcohol and deionization
Water respectively cleans it, and freeze-drying obtains electronegative MoCdS3Composite material.
Preferably, the specific steps of the step S2 are as follows:
(1) by electronegative MoCdS obtained in step S13It is molten that composite material is scattered in cetyl trimethylammonium bromide
In liquid, stirring；
(2) it is centrifuged after stirring in step (1), discards supernatant liquid, obtain sediment, and carried out to it with deionized water
Cleaning, freeze-drying, obtains organically-modified MoCdS3Composite material.
Preferably, the reaction temperature of the hydrothermal synthesis in the step (2) is 200 DEG C~240 DEG C, more preferably 220 DEG C；
The reaction time of hydrothermal synthesis is 10~14 hours, more preferably 12 hours.
Preferably, the number with washes of absolute alcohol in the step (3) is 3~7 times, more preferably 5 times；Spend from
The number of sub- water cleaning is 3~7 times, more preferably 5 times.
Preferably, the speed of the stirring in the step (1) is 400~800rpm, more preferably 600rpm；Stirring when
Between be 10~14 hours, more preferably 12 hours.
A kind of organically-modified MoCdS of the invention3Composite material, using the organically-modified MoCdS of above-mentioned synthesis3Composite material
Method synthesize to obtain.
The organically-modified MoCdS of above-mentioned synthesis of the invention3Application of the composite material in the sewage treatment containing BPA/MO.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) the organically-modified MoCdS of a kind of synthesis of the invention3The method of composite material, using Thiomolybdate and cadmium salt,
One step hydro thermal method synthesizes to obtain electronegative MoCdS3Composite material, then using cetyl trimethylammonium bromide to obtaining
Electronegative MoCdS3Composite material progress is organically-modified, obtains organically-modified electronegative MoCdS3Composite material.MoCdS3
In composite material, CdS and MoS2Exist with a kind of structure of class two-dimensional hetero-junctions, CdS and MoS2Insertion mutually has shorter
Photoelectron transfer path and higher photochemical stability, to improve the light utilization efficiency and composite material of photocatalytic process
Anti-light corrosive power, improve the degradation rate to BPA/MO；And cetyl trimethylammonium bromide is modified
MoCdS3Due to the presence of organic layer, to promote absorption of the composite material to BPA/MO, BPA/MO is improved to MoCdS3It produces
The utilization rate of raw active oxygen radical improves degradation efficiency；
(2) the organically-modified MoCdS of a kind of synthesis of the invention3The method of composite material, is embedded in by one-step synthesis
Formula class two-dimensional structure composite hetero-junctions, in the form of this existing for MoCdS3In conjunction with even closer, so that in composite material
Cd2+It is not easy to be released, not will cause secondary pollution, can make up for it the defect of traditional substep synthetic method, while guaranteeing to degrade
Efficiency realizes environmental-friendly purpose；
(3) the organically-modified MoCdS of a kind of synthesis of the invention3The method of composite material, by a step hydrothermal synthesis mistake
The mass ratio of reaction raw materials Thiomolybdate and cadmium salt in journey, hydrothermal synthesis reaction condition optimize so that reaction process
In due to metathesis generate Cd2+Replace the Mo in molybdenum disulfide4+, to generate the MoCdS for having negative electricity3Composite material；
(4) the organically-modified MoCdS of a kind of synthesis of the invention3The method of composite material passes through cetyl trimethyl bromine
Change the modified electronegative MoCdS of ammonium3Composite material, using cetyl trimethylammonium bromide to the adsorption capacity of organic substance,
So that more BPA/MO are adsorbed onto material surface, so that the probability of BPA and material impacts is improved, to improve light reaction effect
Rate；
(5) the organically-modified MoCdS of a kind of synthesis of the invention3Composite material, since cetyl trimethylammonium bromide has
The presence of machine layer shows good settling property, is conducive to be separated by solid-liquid separation, to realize MoCdS3The repetition of composite material
It utilizes；
(6) the organically-modified MoCdS of a kind of synthesis of the invention3Composite material, the organically-modified method are to be used in for the first time
In the modification of semiconductor light-catalyst.It can not only realize the fast degradation under visible light illumination condition to BPA/MO, and
Also have the advantages that synthetic method is simple, anti-light corrosive power is strong, stability is high, reusable rate is high, continuously repeats utilization
After five times, still reach 95% or more BPA/MO degradation efficiency, suitable in the sewage treatment containing BPA/MO.
Detailed description of the invention
Fig. 1 is organically-modified MoCdS of the invention3Composite material (HDTMA-MoCdS3) synthesis path schematic diagram；
Fig. 2 is MoCdS of the invention3And HDTMA-MoCdS3Photo in kind；
Fig. 3 a is MoCdS of the invention3TEM figure；
Fig. 3 b is MoCdS of the invention3HRTEM figure；
Fig. 3 c is HDTMA-MoCdS of the invention3TEM figure；
Fig. 4 is HDTMA-MoCdS of the invention3XRD diagram；
Fig. 5 is electronegative MoCdS of the invention3And HDTMA-MoCdS3Infrared spectrogram；
Fig. 6 a is HDTMA-MoCdS of the invention3X-ray photoelectron spectroscopy；
Fig. 6 b-d is respectively HDTMA-MoCdS of the invention3Middle molybdenum element, cadmium element, element sulphur x-ray photoelectron energy
Spectrum；
Fig. 7 (on) it is CdS, MoS in the present invention2、MoCdS3、HDTMA-MoCdS3Uv absorption spectra；
Fig. 7 (under) it is CdS, MoS in the present invention2、MoCdS3、HDTMA-MoCdS3It is converted according to Kubelka-Munk formula
Band gap diagram；
Fig. 8 a is CdS, MoS in the present invention2、MoCdS3、HDTMA-MoCdS3Photoelectricity flow graph；
Fig. 8 b is MoS in the present invention2、MoCdS3、HDTMA-MoCdS3Impedance diagram；
Fig. 8 c is the impedance diagram of CdS in the present invention；
Fig. 9 a is BPA degradation kinetics curve figure in the present invention；
Fig. 9 b is MO degradation kinetics curve in the present invention；
Fig. 9 c is to reuse HDTMA-MoCdS of the invention3The efficiency chart of degradation BPA；
Figure 10 a is HDTMA-MoCdS in the present invention3Cd2+Burst size；
Figure 10 b is the Cd of CdS in the present invention2+Burst size；
Figure 11 is HDTMA-MoCdS of the invention3Reuse the infrared spectrogram of front and back；
Figure 12 a is CdS, MoS in the present invention2、MoCdS3And HDTMA-MoCdS3Electron paramagnetic resonance spectrogram；
Figure 12 b is CdS, MoS in the present invention2、MoCdS3And HDTMA-MoCdS3Free radical figure.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Hereafter to the detailed description of exemplary embodiment of the present invention with reference to attached drawing, although these exemplary embodiment quilts
Sufficiently describe in detail so that those skilled in the art can implement the present invention, it is to be understood that can realize other embodiments and
Can without departing from the spirit and scope of the present invention to the present invention various changes can be made.Hereafter to the embodiment of the present invention
More detailed description is not limited to required the scope of the present invention, and just to be illustrated and do not limit pair
The description of the features of the present invention and feature to propose to execute best mode of the invention, and is sufficient to make those skilled in the art
It can implement the present invention.Therefore, the scope of the invention is only defined by the appended claims.
The organically-modified MoCdS of a kind of synthesis of the invention3The method of composite material, comprising the following steps:
S1, mass ratio is dissolved in dimethyl acetamide for 1.5~2.0 four thio ammonium molybdate and cadmium nitrate, stirring is straight
To being completely dissolved, clear four thio ammonium molybdate and cadmium nitrate mixed liquor are obtained；Then by obtained four thio ammonium molybdate and nitre
Sour cadmium mixed liquor moves in hydrothermal reaction kettle, in the case where hydrothermal temperature is 200 DEG C~240 DEG C, more preferably at 220 DEG C,
Reaction 10~14 hours, more preferably 12 hours, obtains electronegative MoCdS3Composite material precipitating；Centrifugation, it is clear to discard upper layer
Liquid collects above-mentioned electronegative MoCdS3Composite material is precipitated and is cleaned respectively to it with dehydrated alcohol and deionized water,
It is wherein 3~7 times, more preferably 5 times with the number of washes of absolute alcohol；It is 3~7 times with the number that deionized water is cleaned, more
It preferably 5 times, is then freeze-dried, obtains electronegative MoCdS3Composite material；
S2, the electronegative MoCdS for obtaining step S13Composite material is scattered in cetyl trimethylammonium bromide solution
In, wherein electronegative MoCdS3The mass ratio of composite material and cetyl trimethylammonium bromide is 3.0~4.0；Then hold
Continuous stirring, the speed of stirring are 400~800rpm, more preferably 600rpm；The time of stirring is 10~14 hours, more preferably
12 hours；It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and carry out cleaning 5 times to it with deionized water, freezing
It is dry, obtain organically-modified MoCdS3Composite material.
A kind of organically-modified MoCdS of the invention3Composite material, using the organically-modified MoCdS of above-mentioned synthesis3Composite material
Method synthesize to obtain.The composite material can be realized the fast degradation under visible light illumination condition to BPA and MO, and the material
The synthetic method of material is simple, anti-light corrosive power is strong, stability is high, reusable rate is high, suitable for containing BPA/MO's
In sewage treatment application.
It is worth noting that cadmium sulfide is a kind of visible light-responded semiconductor catalysis material, forbidden bandwidth 2.4eV,
It is visible light-responded to arrive 560nm.Molybdenum disulfide is a kind of photocatalytic semiconductor material with class graphene layer structure, is prohibited
Bandwidth 1.6eV, light abstraction width almost cover entire visible region.Using four thio ammonium molybdate and cadmium nitrate as Material synthesis light
It is catalyzed semiconductor composite MoCdS3, the semiconductor material produces photohole and electronics pair under illumination condition；Photoproduction
Hole can activating proton and hydrone generate hydroxyl radical free radical, light induced electron can activating oxygen generate superoxide radical.
The cadmium sulfide and molybdenum disulfide composite material that the present invention is synthesized by one step hydro thermal method are tight with a kind of combination
The form of close class two-dimensional composite heterogenous junction exists, while there is also the Cd generated due to metathesis2+Replace molybdenum disulfide
In Mo4+, so that composite material is per se with negative electricity.The presence of heterojunction structure makes cadmium sulfide and molybdenum disulfide conduction band and valence band
The trend of the oriented low conduction band of the light induced electron of upper generation and hole and valence band migration, to play to light induced electron and hole more
Good centrifugation improves utilization rate to extend the service life in light induced electron and hole.
In addition, closely class two-dimensional hetero-junctions can be more stabilized but also the material is not easy by photoetch.Cd2+
Replace Mo4+After make negative electricity on composite material band, so as to easily by have amino positive charged group cetyl front three
Base ammonium bromide is modified.Modified MoCdS3Composite material can enhance to BPA (bisphenol-A)/MO (methyl orange) adsorption capacity,
So that more BPA/MO are adsorbed onto material surface, the probability of BPA/MO and material collision are improved, is urged to promote light
Change the progress of degradation reaction, improves degradation efficiency.
It is worth further illustrating, MoCdS in the present invention3It is the embedded class two-dimensional structure obtained by one-step synthesis
Composite heterogenous junction, MoCdS existing for this form3In conjunction with even closer, so that the Cd in material2+It is not easy to be released, no
It will cause secondary pollution, can make up for it the defect of traditional substep synthetic method, while guaranteeing degradation efficiency, realize environmental-friendly
Purpose.And cetyl trimethyl ammonia bromide is applied to the organically-modified of semiconductor light-catalyst for the first time by the present invention, is passed through
MoCdS after organically-modified3It not only shows to the stronger absorption of organic pollutant and catalytic performance, while also showing to be easy to
Sedimentation, to be conducive to be separated by solid-liquid separation the recycling, it can be achieved that material.
Embodiment 1
As shown in Figure 1, a kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, including following step
It is rapid:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
Take 10mL MoCdS3And HDTMA-MoCdS3As for the water that 10mL in glass tube, is added, rotor is added and stirs two points
Clock stands one minute, takes pictures, HDTMA-MoCdS3Compare MoCdS3Better settling property is shown, as shown in Figure 2.
Embodiment 2
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3).Using transmission electron microscope (TEM, JWM-200CX,
JEOL, Japan) observation have HDTMA-MoCdS3Surface structure, as shown in Figure 3.It is same in the composite material of the bright synthesis of TEM chart
When have CdS and MoS2Structure cell.
Embodiment 3
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
CdS, MoS are observed using x-ray diffractometer (XRD, Phillips, Panalytical, Netherlands)2With
MoCdS3Crystal structure.As shown in figure 4, XRD is the result shows that MoCdS3CdS and MoS are existed simultaneously in composite material2。
Embodiment 4
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
Organically-modified MoCdS is characterized using Fourier Transform Infrared Spectrometer (FTIR, Bruker tensor 27)3It is multiple
Condensation material.As shown in figure 5, there is the characteristic absorption of apparent cetyl trimethylammonium bromide at 2843cm-1 and 2913cm-1
Peak, it was demonstrated that organically-modified success.
Embodiment 5
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
MoCdS is analyzed using x-ray photoelectron spectroscopy (PHI5000Versaprobe, UIVAC-PHI, Japan)3In
The state and chemical bond of Cd, Mo, S.As shown in Fig. 6 a-d, compared to individual CdS and MoS2, MoCdS3In exist simultaneously Cd2+
(Cd 3d5/2, Cd 3d3/2), S2-(S 2p1/2, S 2p3/2) and Mo4+(Mo 3d3/2, Mo 3d5/2), illustrates in MoCdS3
CdS and MoS are existed simultaneously in composite material2。
Embodiment 6
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
CdS, MoS are analyzed using ultraviolet spectra (Lambda 750, PerkinElmer)2, MoCdS3And HDTMA-MoCdS3
Light abstraction width.As Fig. 7 (on) shown in, the light abstraction width of CdS can achieve 550nm, MoS2Light abstraction width can be with
Reach 760nm, MoCdS3The visible absorption range and MoS of composite material2It is almost the same.According to Kubelka-Munk formula meter
Obtained CdS, MoS2、MoCdS3And HDTMA-MoCdS3Forbidden bandwidth is respectively 2.25eV, 1.44eV and 1.46eV, such as Fig. 7
(under) shown in.
Embodiment 7
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Solution water is scattered in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
CdS, MoS are analyzed using electrochemical workstation (CHI660D, Shanghai Chen hua Ltd., China)2,
MoCdS3And HDTMA-MoCdS3Photoelectric current and impedance.As shown in Figure 8 a, under 500W xenon lamp pulsed light photograph, MoCdS3With
HDTMA-MoCdS3Photo-current intensity be significantly stronger than MoS2And CdS.As shown in Fig. 8 b-c, MoCdS3And HDTMA-MoCdS3's
Impedance is minimum, and CdS impedance is maximum.
Embodiment 8
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
Using the organically-modified MoCdS of the present embodiment3Composite material carries out BPA degradation, the steps include: to take the concentration be
100mg/LBPA aqueous solution 2mL in quartzy light reaction pipe (d=2cm, h=10cm), and be added 18mL ultrapure water and
0.01gHDTMA-MoCdS3Composite material obtains reaction mixture；It the use of concentration is 1mM HCl and 1mM NaOH reaction is mixed
The pH for closing object is adjusted to 6, and photolysis is carried out under 26 DEG C of reaction temperature, reaction time 220min.
MoCdS will be added respectively3、CdS、MoS2It is tested as a control group with blank (direct photolysis), other experiment items
Part and the organically-modified MoCdS of addition3(HDTMA-MoCdS3) experiment condition it is consistent.
The kinetic curve and product kinetic curve of BPA as illustrated in fig. 9, retouched with pseudo first order reaction by kinetic reaction
It states, model Ct/C0=exp (- kobsT), CtRefer to the concentration of the BPA of reaction time t, C0Refer to the initial concentration of BPA, kobsRefer to real
The reaction rate constant tested is fitted to obtain CdS, MoS2、MoCdS3And HDTMA-MoCdS3Pseudo-first order reaction kinetics speed
Rate constant kobs(min-1) it is respectively 0.000153,0.00519,0.00699 and 0.0133min-1。
Using the organically-modified MoCdS of the present embodiment3Composite material carries out MO degradation, the steps include: to take the concentration be
100mg/LMO aqueous solution 2mL in quartzy light reaction pipe (d=2cm, h=10cm), be added 18mL ultrapure water and
0.01gHDTMA-MoCdS3Composite material obtains reaction mixture；It the use of concentration is 1mM HCl and 1mM NaOH reaction is mixed
The pH for closing object is adjusted to 6, and photolysis is carried out under 26 DEG C of reaction temperature, reaction time 220min.
MoCdS will be added respectively3、CdS、MoS2It is tested as a control group with blank (direct photolysis), other experiment items
Part and the organically-modified MoCdS of addition3Experiment condition it is consistent.
The kinetic curve and product kinetic curve of MO as shown in figure 9b, retouched with pseudo first order reaction by kinetic reaction
It states, model Ct/C0=exp (- kobsT), CtRefer to the concentration of the MO of reaction time t, C0Refer to the initial concentration of MO, kobsRefer to experiment
Obtained reaction rate constant is fitted to obtain CdS, MoS2、MoCdS3And HDTMA-MoCdS3Pseudo-first order reaction kinetics rate
Constant kobs(min-1) it is respectively 0.00218,0.00528,0.00996 and 0.0159min-1。
Embodiment 9
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
In order to study organically-modified MoCdS3Reusing, will be organically-modified after BPA degradation reaction in embodiment 8
MoCdS3Drying recycling is filtered, BPA degradation experiment same as Example 8 is carried out, continuously repeats aforesaid operations five times.Such as Fig. 9 c
Shown, continuous five reuses, the material still reaches 95 or more percent BPA degradation efficiency in 220min.
Embodiment 10
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
In order to detect organically-modified MoCdS3Stability, take CdS and HDTMA-MoCdS3Progress five times is continuously repeated respectively
The supernatant liquid after BPA degradation reaction in embodiment 8, measures Cd therein2+Content.As illustrated in figures 10 a-b, degradation is anti-every time
Ying Hou, organically-modified MoCdS3Cd2+Burst size is significantly lower than CdS.
Embodiment 11
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
In order to detect organically-modified MoCdS3Stability, by reuse five times after organically-modified MoCdS3Not by
The organically-modified MoCdS utilized3Infrared test is done respectively.As shown in figure 11, cetyl trimethyl bromine after reusing five times
The characteristic absorption peak intensity for changing ammonium does not weaken still, this shows that there is no destroyed organic modifiers.
Embodiment 11
A kind of organically-modified MoCdS of synthesis of the present embodiment3The method of composite material, comprising the following steps:
(1) four thio ammonium molybdate (72.6mg) and cadmium nitrate (43.1mg) are dissolved in dimethyl acetamide (33.3ml),
It is stirred continuously until that four thio ammonium molybdate, cadmium nitrate all dissolve, obtains clear four thio ammonium molybdate and cadmium nitrate mixed liquor；
Then the dimethylacetamide solution that four thio ammonium molybdate and cadmium nitrate mix is moved in 100ml hydrothermal reaction kettle, in hydro-thermal
Reaction temperature is to react 12 hours at 220 DEG C, and hydrothermal synthesis obtains electronegative MoCdS3Precipitating；Centrifugation, discards supernatant liquor,
Collect above-mentioned electronegative MoCdS3It precipitates and it is cleaned respectively 5 times with dehydrated alcohol and deionized water, is freeze-dried spare；
(2) by electronegative MoCdS obtained in step (1)3It is configured to the MoCdS that concentration is 2g/L3Aqueous solution takes
The MoCdS of 100ml3Aqueous dispersion in 2.16g/L cetyl trimethylammonium bromide (HDTMA) aqueous solution of 25ml,
Obtain dispersion liquid of the MoCdS in HDTMA solution；Then persistently stir above-mentioned dispersion liquid 12 hours, mixing speed 600rpm；
It is centrifuged after stirring, discards supernatant liquid, obtain sediment, and cleaning 5 times is carried out to sediment with deionized water, freezing is dry
It is dry, obtain organically-modified MoCdS3Composite material (HDTMA-MoCdS3)。
The drop of BPA is explained using electron paramagnetic resonance spectrum (EPR, Bruker X-band A300-6/1) capture free radical
Solve mechanism, reaction condition are as follows: under 500W xenon lamp, 0.5g/L CdS, MoS will be contained2、MoCdS3Or HDTMA-MoCdS3
And 200 μ L solution of 20mM hydroxyl radical free radical capturing agent dimethyl pyrrole nitrogen oxides (DMPO) are respectively in aqueous solution and methanol
It is reacted in solution, reaction time 5min.The relative parameters setting of electron paramagnetic resonance spectral instrument are as follows: central field:
3518G；Sweep length: 100G；Microwave frequency: 9.87GHz；Modulation width: 1G；Modulating frequency: 100kHz；Microwave energy:
20mW；Receiver gain: 1.0 × 103.As shown in Figure 12 a-b, it is detected simultaneously by hydroxyl radical free radical and superoxide radical signal,
Explain the free radical type that main function is played in contaminant degradation reaction.
Claims (10)
1. a kind of organically-modified MoCdS of synthesis3The method of composite material, comprising the following steps:
S1, using Thiomolybdate and cadmium salt, one step hydro thermal method synthesizes to obtain electronegative MoCdS3Composite material；
S2, using cetyl trimethylammonium bromide to electronegative MoCdS obtained in step S13Composite material carries out organic
It is modified, obtain organically-modified MoCdS3Composite material.
2. a kind of organically-modified MoCdS of synthesis according to claim 13The method of composite material, it is characterised in that: described
Thiomolybdate in step S1 is four thio ammonium molybdate, and cadmium salt is the matter of cadmium nitrate, wherein four thio ammonium molybdate and cadmium nitrate
Amount is than being 1.5~2.0.
3. a kind of organically-modified MoCdS of synthesis according to claim 13The method of composite material, it is characterised in that: described
Electronegative MoCdS in step S23The mass ratio of composite material and cetyl trimethylammonium bromide is 3.0~4.0.
4. a kind of organically-modified MoCdS of synthesis according to claim 13The method of composite material, it is characterised in that: described
The specific steps of step S1 are as follows:
(1) Thiomolybdate and cadmium salt are dissolved in dimethyl acetamide, stirring until be completely dissolved, obtain Thiomolybdate and
The mixed liquor of cadmium salt；
(2) mixed liquor of Thiomolybdate obtained in step (1) and cadmium salt is moved in hydrothermal reaction kettle, hydrothermal synthesis obtains
Electronegative MoCdS3Composite material precipitating；
(3) electronegative MoCdS obtained in collection step (2)3Composite material precipitating, and with dehydrated alcohol and deionization moisture
Other to clean to it, freeze-drying obtains electronegative MoCdS3Composite material.
5. a kind of organically-modified MoCdS of synthesis according to claim 13The method of composite material, it is characterised in that: described
The specific steps of step S2 are as follows:
(1) by electronegative MoCdS obtained in step S13Composite material is scattered in cetyl trimethylammonium bromide solution,
Stirring；
(2) it is centrifuged after stirring in step (1), discards supernatant liquid, obtain sediment, and carried out clearly to it with deionized water
It washes, is freeze-dried, obtains organically-modified MoCdS3Composite material.
6. a kind of organically-modified MoCdS of synthesis according to claim 43The method of composite material, it is characterised in that: described
The reaction temperature of hydrothermal synthesis in step (2) is 200 DEG C~240 DEG C, and the reaction time of hydrothermal synthesis is 10~14 hours.
7. a kind of organically-modified MoCdS of synthesis according to claim 43The method of composite material, it is characterised in that: described
The number with washes of absolute alcohol in step (3) is 3~7 times, is 3~7 times with the number that deionized water is cleaned.
8. a kind of organically-modified MoCdS of synthesis according to claim 53The method of composite material, it is characterised in that: described
The speed of stirring in step (1) is 400~800rpm, and the time of stirring is 10~14 hours.
9. a kind of organically-modified MoCdS3Composite material, it is characterised in that: use synthesis of any of claims 1-8
Organically-modified MoCdS3The method of composite material synthesizes to obtain.
10. the organically-modified MoCdS of synthesis according to claim 93Composite material is in the sewage treatment containing BPA/MO
Using.
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| CN115770616A (en) * | 2022-11-04 | 2023-03-10 | 武汉科技大学 | CTAB-MoS x -CdS composite photocatalyst and preparation method and application thereof |
| CN116328791A (en) * | 2023-03-21 | 2023-06-27 | 中南大学 | Photocatalyst, and preparation method and application thereof |
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