CN116621718A - Molybdenum selenium cluster compound containing transition metal complex ions and solvothermal preparation method and application thereof - Google Patents
Molybdenum selenium cluster compound containing transition metal complex ions and solvothermal preparation method and application thereof Download PDFInfo
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- CN116621718A CN116621718A CN202310471653.7A CN202310471653A CN116621718A CN 116621718 A CN116621718 A CN 116621718A CN 202310471653 A CN202310471653 A CN 202310471653A CN 116621718 A CN116621718 A CN 116621718A
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- selenium
- molybdenum
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 82
- DORQJBTVNDGTEY-UHFFFAOYSA-N selanylidenemolybdenum Chemical compound [Se].[Mo] DORQJBTVNDGTEY-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 150000002500 ions Chemical class 0.000 title claims abstract description 49
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 42
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011669 selenium Substances 0.000 claims abstract description 137
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 29
- 229910052711 selenium Inorganic materials 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000011733 molybdenum Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 12
- 239000000975 dye Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001782 photodegradation Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 239000011734 sodium Substances 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- 239000013078 crystal Substances 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 13
- -1 Molybdenum chalcogenides Chemical class 0.000 description 10
- 238000011160 research Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 150000002892 organic cations Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- 238000004847 absorption spectroscopy Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000005580 one pot reaction Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229940065287 selenium compound Drugs 0.000 description 4
- 150000003343 selenium compounds Chemical class 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011011 black crystal Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 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 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/65—Metal complexes of amines
-
- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The invention relates to a molybdenum selenium cluster compound containing transition metal complex ions, and a solvothermal preparation method and application thereof. The structural general formula of the molybdenum selenium cluster compound is as follows: [ M (en) 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2 Or [ M (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2 M is Mn, co or Ni; en is ethylenediamine and dien is diethylenetriamine. The method directly synthesizes the molybdenum selenium cluster compound containing the transition metal complex ions by one-step solvothermal reaction, simplifies the synthesis steps and improves the synthesis efficiency and the product yield.
Description
Technical Field
The invention relates to the technical field of molybdenum-selenium cluster compounds, in particular to a molybdenum-selenium cluster compound containing transition metal complex ions, and a solvothermal preparation method and application thereof.
Background
The preparation and properties of metal chalcogenides have attracted considerable research interest due to their important role in energy conversion, generation and storage applications in fields including catalysis, semiconductors, photovoltaics, batteries and photochemical synthesis. Molybdenum chalcogenides (S, se) have the characteristics of narrow semiconductor energy, low free energy of hydrogen adsorption gibbs, and are one of the most widely used catalysts in the hydrodesulfurization of petroleum, being the most promising inexpensive catalyst for the electrochemical and photochemical production of hydrogen from water instead of platinum. Meanwhile, due to the existence of various variable valence of +4, +5, +6 and the like, molybdenum has rich reaction chemical properties and easy-to-obtain oxidation-reduction interconversion characteristics, and the molybdenum chalcogenides have wide application prospects in the fields of catalysis and sulfur-based batteries. At present, a series of structural formulas [ Mo ] are synthesized and structurally characterized 2 X 2 (μ-E) 2 (E m E n ) 2 ] 2– (x=o, S, se; e=s, se; m, n=1-4), the counter cation of which may be a metal ion or an organic cation. [ Mo 2 X 2 (μ-E) 2 (E m E n )] 2– Is structurally characterized by containing one [ Mo ] 2 X 2 (μ-E) 2 )] 2+ Double molybdenum core and two polysulfide ions S n 2– Or polyselenium Se n 2– (n=1-4). Double molybdenum core [ Mo 2 X 2 (μ-E) 2 )] 2+ By two MoX through two μ -E 2– The bridge group ligand is formed by connecting, each mu-E 2– The ligand is linked to both Mo atoms. A large number of [ Mo ] have been synthesized 2 O 2 (μ-S) 2 (S m S n ) 2 ] 2– Molybdenum-sulfur cluster compounds, e.g. molybdenum-sulfur cluster compounds K [ (L) Mo) containing alkali metal ions 2 O 2 (μ-S) 2 (S 2 ) 2 ](L is leu, met, thr, ser), molybdenum sulfur cluster compound containing organic cation [ (CH) 3 ) 4 N] 2 [Mo 2 O 2 (μ-S) 2 (S 2 ) 2 ]、[(CH 3 ) 4 N] 2 [Mo 2 O 2 (μ-S) 2 (S 2 )(S 4 )]、[(CH 3 ) 4 N] 2 [Mo 2 O 2 (μ-S) 2 (S 2 )(S 4 )]·CH 3 CN and [ Ph ] 4 P] 2 [Mo 2 O 2 (μ-S) 2 (S 2 ) 2 ]And molybdenum sulfur cluster compound [ Mo ] containing organic ligand 2 O 2 (μ-S) 2 (DMF) 3 ]、Mo 2 O 2 (μ-S) 2 (Et 2 dtc) 2 (dtc is a dithiocarbamate). Compared with molybdenum-sulfur cluster compound, [ Mo ] 2 O 2 (μ-Se) 2 (Se n ) 2 ] 2– The research of the binuclear molybdenum selenium cluster compound is relatively few, and only few examples of the binuclear molybdenum selenium cluster compound are reported at present. These molybdenum selenium clusters can be classified into different types depending on their counter cations and polyselenium ions.
Reports on molybdenum selenium cluster compound containing alkali metal ion
(1) In 1990, henkel produced Na-containing reaction in multiple steps + Molybdenum selenium cluster compound of ions. Respectively by (NH) 4 ) 6 Mo 7 O 24 ·6H 2 O and NaHSe are used as molybdenum source and selenium source, cys (Cys=L (+) -cysteine) is used as organic ligand, and molybdenum selenium cluster compound Na [ (CH) is prepared 3 ) 4 N][Mo 2 O 2 (μ-Se) 2 (Cys) 2 ]·7H 2 O, which is synthesized by multiple steps, has a low yield of only 33%. (see: G.Henkel, G.Kampmann, B.Krebs, G.J.Lamprecht, M.Nasreldin and A.G.Sykes, J.Chem.Soc., chem.Commun.,1990,15,1014-1016.).
(2) In 1993, eichhorns utilized two-step reverseThe method prepares the K-containing + Molybdenum selenium cluster compound of ions. Firstly Mo is used 2 (O 2 CCH 3 ) 4 (O 2 CCH 3 Acetate) and K 2 Se 4 Reacting in ethylenediamine for 3 hours, filtering to obtain clear liquid, adding crown ether 2,2-crypt (2, 2-crypt=1, 4,7,10,13, 16-hexaoxacyclooctadecane) into the filtrate, filtering after the reaction is finished, and standing the filtrate for 6 days to obtain black crystal [ K (2, 2-crypt)] 2 [Mo 2 O 2 (μ-Se) 2 (Se 2 )]The yield was 55%. Synthetic raw material K 2 Se 4 Is prepared by the reaction of potassium and selenium in liquid ammonia under the protection of nitrogen atmosphere. The DMSO and DMF solvents used in the synthesis should be free of moisture, and distilled after drying the molecular sieves before use. (see: B.W.Eichborn, J.R.Gardner, A.N.Ziebah, K.J.AhmetI and S.G.Bott, inorg.Chem.,1993,32,5412-5414.).
Second, reports on molybdenum selenium cluster compound containing organic cation
(1) In 1996, mak prepared molybdenum selenium cluster compound containing organic cation by two-step reaction method. Firstly Mo (CO) 6 And K 2 Se 4 Reacting in ethanol at 100deg.C for 72 hr to obtain black powder, and mixing with Et 4 NCl·H 2 O in ethanol to prepare the compound (Et 4 N) 2 [(Mo 2 O 2 Se 6 ) 0.20 ((Mo 2 O 2 Se 6 ) 0.18 (Mo 2 O 2 Se 6 ) 0.62 ]The molybdenum selenium anion cluster is composed of [ Mo ] 2 O 2 (μ-Se) 2 )] 2+ Core and polyselenium Se 2 2– 、Se 3 2– 、Se 4 2– The composition wherein the occupancy of the polyselenium ions was 0.20, 0.18 and 0.62, respectively. The preparation of the compound requires two steps of reaction, has low yield, and uses highly toxic Mo (CO) 6 As a molybdenum source. And synthetic raw material K 2 Se 4 Is prepared under severe conditions by reacting potassium and selenium simple substances with stoichiometric ratio in an autoclave at 400 ℃ for 5 hours under the protection of nitrogen atmosphere to obtain K 2 Se 4 . (see: g.c. guo andT.C.W.Mak, inorg.Chem.,1998,37,6538-6540.).
(2) 2022 Elliott prepared a solution Containing (CH) under nitrogen by a multi-step reaction method 3 ) 4 N + Cationic molybdenum selenium cluster compounds. Adding a certain amount of selenium powder into water, introducing nitrogen into the water to remove oxygen in the water (i.e. degassing), and adding NaBH 4 The degassing with nitrogen was continued and the reaction was carried out at 50℃for 40 minutes. Then, ammonium heptamolybdate (NH) 4 ) 6 Mo 7 O 24 After stirring overnight under nitrogen flow, filtration was performed. To the filtrate was added tetramethyl ammonium chloride (CH 3 ) 4 NCl, a dark brown precipitate formed, which was washed with cold water, cold ethanol and diethyl ether, respectively. Dissolving the precipitate in DMF to form saturated solution, standing for several weeks to obtain brown black crystal [ (CH) 3 ) 4 N] 2 [Mo 2 O 2 (μ-Se) 2 (Se 2 ) 2 ]. In MoO 3 Substitution (NH) 4 ) 6 Mo 7 O 24 By Se and Na 2 Se 2 The same synthesis method is used for replacing selenium powder, and finally the [ (CH) is prepared by recrystalization in acetonitrile/diethyl ether mixed solvent 3 ) 4 N] 2 [Mo 2 O 2 (μ-Se) 2 (Se 2 )(Se 4 )] 0.5 [Mo 2 O 2 (μ-Se) 2 (Se 2 )(Se 3 )] 0.25 [Mo 2 O 2 (μ-Se) 2 (Se 2 )] 0.25 . (see: A.Elliott, J.McAllister, L.Masaityte, M.S.Centellas, D.L.Long, A.Y.Ganin, Y.F.Song, C.Bo and H.N.Miras, chem.Commun.,2022,58,6906-6909.).
Third report on molybdenum selenium cluster Compound containing organic selenium ligand
(1) In 2006, nguyen used MoCl 5 And% i Pr 2 PSe) 2 Se( i Pr=isopropyl) in ethanol for 1 hour to form yellow precipitate, washing the precipitate with ethanol, and re-crystallizing in dichloromethane to obtain brown crystal [ Mo 2 O 2 (μ-Se) 2 (Se 2 P i Pr 2 ) 2 ]The molybdenum selenium cluster compound contains two organic selenium ligands Se 2 P i Pr 2 . Selenium source [ ] i Pr 2 PSe) 2 Se is made by NEt 3 、 i Pr 2 PCl、HSiCl 3 Se is used as a raw material, and is synthesized by two steps of reaction in a hexane solvent and a toluene solvent and finally recrystallization in toluene. [ Mo 2 O 2 (μ-Se) 2 ( i Pr 2 PSe 2 ) 2 ]And% i Pr 2 PSe) 2 The Se synthesis needs an inert environment, and the whole process is carried out in a standard Schlenk anhydrous and anaerobic double-row-pipe operation system. (see: C.Q.Nguyen, A.Adeogun, M.Afzaal, M.A.Malik and P.O.Brien, chem.Commun.,2006,20,2182-2184;C.Q.Nguyen,A.Adeogun,M.Afzaal,M.A.Malik and P.O.Brien,Chem.Commun, 2006,20,2179-2181).
In view of the foregoing, molybdenum chalcogenides are an important component of metal chalcogenides, and research in this area has been receiving attention. More binuclear molybdenum-sulfur compounds have been synthesized and structurally characterized, but compared with the molybdenum-sulfur compounds, the molybdenum-selenium compounds with the binuclear structure have few researches, only few molybdenum-selenium compounds have been reported in the literature, counter cations of the molybdenum-selenium compounds are alkali metal ions or organic cations, and molybdenum-selenium compounds taking transition metal complex ions as counter ions are not reported in the literature so far.
At present, molybdenum selenium cluster compounds are prepared by taking volatile organic compounds as solvents in a non-aqueous and non-oxygen operation system through multi-step reactions. Firstly, mo (CO) is prepared 6 、(NH 4 ) 6 Mo 7 O 24 、MoCl 5 、K 2 Se 4 、NaHSe、Na 2 Se 2 、( i Pr 2 PSe) 2 Se and other compounds as intermediates for synthesizing molybdenum selenium cluster compounds (molybdenum source and selenium source), and the preparation of the intermediates needs to be carried out under anhydrous and anaerobic inert or high temperature and other severe conditions, such as Mo (CO) 6 And% i Pr 2 PSe) 2 Se is prepared by preparing Se in N 2 Completed under the protection of gas, K 2 Se 4 And Na (Na) 2 Se 2 Is prepared by reacting at 400 ℃ for 5 hours under nitrogen atmosphere. Secondly, the synthesis of the molybdenum selenium cluster compound is usually carried out in volatile organic solvents such as acetonitrile, diethyl ether, toluene, methylene dichloride and the like, and the multi-step operation processes such as repeated extraction, precipitation, crystallization, recrystallization and the like are required by using the organic solvents, and the solvents are usually subjected to water removal treatment such as distillation and the like before being used, so that energy sources are consumed, and the environment is not protected. At present, the molybdenum selenium cluster compound prepared and researched by people takes alkali metal ions and organic cations as counter cations, the research of the molybdenum selenium cluster compound containing transition metal complex ions is not reported in the literature, and the research of preparing the molybdenum selenium cluster compound by one-step reaction is not reported in the literature.
At present, a molybdenum selenium cluster compound with alkali metal ions and organic cations as counter cations is synthesized by taking volatile organic compounds as solvents. The reported disadvantages of molybdenum selenium cluster preparation are: (1) Requires the first synthesis of K 2 Se 4 、NaHSe、Na 2 Se 2 、( i Pr 2 PSe) 2 Selenium compounds such as Se and the like are used as preparation raw materials (selenium sources), the preparation of the compound selenium sources is carried out under the harsh conditions of anhydrous and anaerobic inertia or high temperature and the like, and the research of directly using elemental selenium powder as the selenium sources is not reported in the literature; (2) Mo (CO) needs to be synthesized first 6 、(NH 4 ) 6 Mo 7 O 24 、MoCl 5 Mo (CO) as a molybdenum source 6 Is a highly toxic substance; (3) The preparation of the molybdenum-selenium cluster compound requires two or more steps of reaction, the general yield is low, and the research on preparing the molybdenum-selenium cluster compound through one-step reaction is not reported in the literature; (4) The preparation of the molybdenum selenium cluster compound is usually carried out under a complex anhydrous and anaerobic inert bar, and a large amount of volatile solvents such as acetonitrile, diethyl ether, toluene, methylene dichloride and the like are required, and the solvents are usually subjected to water removal treatment such as distillation and the like before being used, so that the energy is consumed, and the environment is not protected. (5) more synthesis steps and lower product yield. For example, na [ (CH) 3 ) 4 N][Mo 2 O 2 (μ-Se) 2 (Cys) 2 ]·7H 2 The O yield was only 33%. Therefore, there is an urgent need to develop a more efficient and environment-friendly production method.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects in the prior art that: (1) Requires the first synthesis of K 2 Se 4 、NaHSe、Na 2 Se 2 、( i Pr 2 PSe) 2 Selenium compounds such as Se and the like are used as preparation raw materials (selenium sources), the preparation of the compound selenium sources is carried out under the harsh conditions of anhydrous and anaerobic inertia or high temperature and the like, and the research of directly using elemental selenium powder as the selenium sources is not reported in the literature; (2) Mo (CO) needs to be synthesized first 6 、(NH 4 ) 6 Mo 7 O 24 、MoCl 5 Mo (CO) as a molybdenum source 6 Is a highly toxic substance; (3) The preparation of the molybdenum-selenium cluster compound requires two or more steps of reaction, the general yield is low, and the research on preparing the molybdenum-selenium cluster compound through one-step reaction is not reported in the literature; (4) The preparation of the molybdenum-selenium cluster compound is usually carried out under a complex anhydrous and anaerobic inert strip, no matter the synthesis of an intermediate product or the preparation, crystallization and recrystallization of the molybdenum-selenium cluster compound need to use a large amount of volatile solvents such as acetonitrile, diethyl ether, toluene, methylene dichloride and the like, the organic solvents have potential safety hazards such as inflammability, easy leakage and the like, and the solvents usually need to be subjected to water removal treatment such as distillation and the like before being used, so that energy is consumed, and the environment protection is also not facilitated. (5) more synthesis steps and lower product yield.
In order to solve the technical problems, the invention provides a molybdenum selenium cluster compound containing transition metal complex ions and a solvothermal preparation method thereof. The preparation method utilizes the chelation coordination effect of ethylene polyamine to synthesize the molybdenum-selenium cluster compound containing transition metal complex ions through one-step reaction under solvothermal conditions, has simple operation, uses simple sodium molybdate inorganic salt and selenium powder as a molybdenum source and a selenium source respectively, avoids the intermediate step of preparing special molybdenum and selenium compounds as the molybdenum source and the selenium source under anhydrous and anaerobic conditions in the traditional method, utilizes simple and easily obtained raw materials, does not need intermediate synthesis steps, and improves the product yield by synthesizing the molybdenum-selenium cluster compound containing transition metal complex ions through one-step reaction. The reaction is not required to be carried out under anhydrous and anaerobic conditions, a large amount of organic solvents used in the traditional preparation method are not required, only two solvents of ethylene polyamine and ethanol are required, and the solvents are not required to be subjected to further water removal treatment. The ethylene polyamine is not only a reaction solvent, but also a chelating ligand of transition metal complex ions, and the ethylene polyamine reacts with the transition metal complex ions in situ to form transition metal complex cations which are used as counter ions of the molybdenum selenium cluster compound, so that the molybdenum selenium cluster compound containing the transition metal complex ions is formed.
The first aspect of the invention aims to overcome the prior art of synthesizing molybdenum selenium cluster compound (NH 4 ) 6 Mo 7 O 24 、Mo 2 (O 2 CCH 3 ) 4 、Mo(CO) 6 、K 2 Se 4 、NaHSe、Na 2 Se 2 、( i Pr 2 PSe) 2 Intermediate products such as Se are used as intermediate steps of molybdenum sources and selenium sources, and the synthesis of the intermediate products is required to be carried out under severe conditions such as high Wen Moshui temperature of 400 ℃, anaerobic conditions and the like, and a large amount of volatile organic solvents such as acetonitrile, toluene, diethyl ether and the like are used.
The second aspect of the invention aims to overcome the defects of the prior art for synthesizing molybdenum selenium cluster compound, wherein the reactions generally need to be carried out at high temperature above 400 ℃ such as K 2 Se 4 ) Or in complex anhydrous, anaerobic operating systems (e.g. Mo (CO) 6 、( i Pr 2 PSe) 2 Se). The final product yield is lower due to the number of synthesis steps.
In order to solve the technical problems, the invention is realized by the following scheme:
the first object of the invention is to provide a molybdenum selenium cluster compound containing transition metal complex ions, wherein the molybdenum selenium cluster compound has a structural general formula: [ M (en) 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2 Or [ M (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2 M is Mn, co or Ni; en is ethylenediamine and dien is diethylenetriamine. [ M (en) 3 ] 2+ And [ M (dien) 2 ] 2+ M in (v) 2+ Coordination numbers are 6, and are octahedral coordination ions. [ Mo 2 O 2 (μ-Se) 2 (Se 2 )] 2– From one [ Mo ] 2 O 2 (μ-Se) 2 )] 2+ Double molybdenum core and two polyselenium Se 2 2– The composition is formed. Cationic nucleus [ Mo ] 2 O 2 (μ-Se) 2 )] 2+ By two MoOs through two mu-Se 2– The bridging group ligand is formed by connecting, each mu-Se 2– The ligand is linked to both Mo atoms.
The second object of the present invention is to provide a method for preparing molybdenum selenium cluster compound containing transition metal complex ion, comprising the following steps: mixing and stirring M-containing salt, a molybdenum source and a selenium source in an ethylene polyamine solvent, and heating for reaction to obtain a molybdenum selenium cluster compound containing transition metal complex ions; m in the M-containing salt is Mn, co or Ni.
In one embodiment of the invention, the M-containing salt is selected from MnCl 2 、CoCl 2 And NiCl 2 One or more of the following.
In one embodiment of the invention, the molybdenum source is selected from Na 2 MoO 4 And/or MoO 3 。
In one embodiment of the invention, the selenium source is selected from Se and/or Na 2 Se。
In one embodiment of the invention, the ethylene polyamine solvent is selected from ethylenediamine and/or diethylenetriamine. The ethylene diamine (boiling point: 116.5 ℃) and diethylenetriamine (boiling point: 207 ℃) have high boiling points, are not easy to volatilize and flammable, avoid environmental pollution, and improve the safety of the preparation process at the same time, and the ethylene polyamine is not only a reaction solvent, but also a chelating agent of transition metal complex ions, and the ethylene polyamine is used as a solvent, has large polarity and strong solubility, and avoids metal selenide MSe (M is transition metal Mn, co, ni) and MoSe 2 The formation of the precipitate is beneficial to the crystallization of the molybdenum selenium cluster compound, thereby forming molybdenum selenium cluster compound crystals and improving the purity of the product; meanwhile, the ethylene polyamine has strong chelating coordination capacity, and is easy to form complex ions with transition metal complex ions, thereby being further combined with molybdenum selenium clustersThe anions combine to form molybdenum selenium cluster compound containing transition metal complex ions. And when the structure of the ethylene polyamine is changed, the structure of the molybdenum selenium cluster anion is kept unchanged, and the semiconductor energy capacity of the product is regulated and controlled by the difference of transition metal complex ions.
In one embodiment of the invention, the molar ratio of the M-containing salt, the molybdenum source and the selenium source is 1:2:6-1:2:8.
In one embodiment of the invention, the conditions of the heating reaction: the reaction temperature is 150-180 ℃ and the reaction time is 4-5 days.
In one embodiment of the invention, the method further comprises the steps of purifying the molybdenum selenium cluster compound containing the transition metal complex ion, wherein the steps are as follows: and after heating, cooling to room temperature, filtering to obtain a filter cake, and washing the filter cake with a detergent to obtain the molybdenum selenium cluster compound containing the transition metal complex ions.
Further, the detergent is selected from ethanol.
The third object of the invention is to provide the molybdenum selenium cluster compound containing the transition metal complex ion or the application of the molybdenum selenium cluster compound containing the transition metal complex ion in catalyzing photodegradation of organic dye.
Further, the organic dye includes, but is not limited to, methylene Blue (MB), crystal Violet (CV), rhodamine B (RhB), methyl Orange (MO), and the like.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the method for synthesizing the molybdenum selenium cluster compound containing the transition metal complex ions is simple, utilizes a solvothermal one-pot method, omits the intermediate step in the traditional synthesis method, and uses cheap and easily obtained Na 2 MoO 4 And Se as a molybdenum source and a selenium source, and preparing a molybdenum-selenium cluster compound containing transition metal complex ions for the first time through one-step solvothermal reaction; a large amount of organic solvent in the conventional synthesis method is not used; the product is convenient to separate and purify, and the yield is high; the molybdenum selenium cluster compound has definite and stable structure; the energy capacity and the semiconductor performance of the molybdenum selenium cluster compound semiconductor can be regulated and controlled through the difference of transition metal complex ions.
(1) The method directly synthesizes the molybdenum selenium cluster compound containing the transition metal complex ions by one-step solvothermal reaction, simplifies the synthesis steps and improves the synthesis efficiency and the product yield.
(2) The method does not use volatile and inflammable organic solvents, avoids environmental pollution, and improves the experimental safety of synthesizing and preparing the molybdenum selenium cluster compound. Any organic solvents other than ethylenediamine (en), diethylenetriamine (dien) and ethanol are not used, and ethylenediamine, diethylenetriamine and ethanol do not require any pretreatment including distillation of water prior to use.
(3) With cheap and easily available Na 2 MoO 4 And Se as molybdenum and selenium sources, without the need to synthesize specific molybdenum and selenium compounds as intermediates, such as Mo (CO) 6 、MoCl 5 、K 2 Se 4 、NaHSe、Na 2 Se 2 、( i Pr 2 PSe) 2 Se and other intermediate products, reduces energy consumption, is cheap and easy to obtain, and is safe and nontoxic. The reactant can directly synthesize the molybdenum selenium cluster compound through one-step solvothermal reaction at a lower temperature (150 ℃), no intermediate step is needed, no anhydrous or anaerobic operation system is needed in the preparation process, no intermediate step is needed, and the synthesis efficiency is improved.
(4) The energy capacity and the semiconductor performance of the molybdenum selenium cluster compound semiconductor can be regulated and controlled through the difference of transition metal complex ions.
(5) The molybdenum selenium cluster compound containing the transition metal complex ion has catalytic activity on photodegradation organic dyes, and the catalytic degradation percentage of the molybdenum selenium cluster compound on organic dyes such as Methylene Blue (MB) and Crystal Violet (CV) reaches more than 88 percent.
(6) And accumulating theoretical and practical experience for designing and synthesizing novel molybdenum selenium cluster compounds.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a schematic illustration of the invention [ M (en) ] 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2 And [ M (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2 Schematic diagram of the preparation process.
FIG. 2 is a schematic diagram of the present invention [ Mn (en) ] 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2 Middle [ Mn (en) 3 ] 2+ (a) And [ Mn (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2 Medium [ Mn (dien) 2 ] 2+ (b) Structure of ion-pairing.
FIG. 3 is a diagram of the [ Mo ] of the present invention 2 O 2 Se 2 (Se 2 ) 2 ] 2- Cluster anion structure diagram.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Embodiment one: [ Mn (en) 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2
MnCl is added to 2 ·4H 2 O (0.099 g, 0.5 mmol), na 2 MoO 4 (0.206 g, 1.0 mmol) and Se (0.237 g, 4.0 mmol) were added to 3 ml of ethylenediamine (en) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reaction kettle of polytetrafluoroethylene and reacted at 150℃for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol, and dried under vacuum to give crystals 0.382 g in 82% yield (as Na 2 MoO 4 Calculation). Elemental analysis: c7.56, H2.48, n 8.84%; theoretical value of element content: C7.73,H 2.59,N 9.01%. Infrared absorption spectrum data (KBr, cm) -1 ): 3417 (s), 3159 (w), 3057 (w), 2923 (m), 2862 (m), 2082 (w), 1574(s), 1491 (m), 1382 (w), 1322 (m), 1151 (w), 1075 (w), 962 (m), 892 (w), 867 (m), 666 (w), 634 (m), 499 (w), 451 (w). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.67eV。
Embodiment two: [ Co (en) 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2
CoCl is to be processed 2 ·6H 2 O (0.119 g, 0)5 mmol), na 2 MoO 4 (0.206 g, 1.0 mmol) and Se (0.237 g, 4.0 mmol) were added to 3 ml of ethylenediamine (en) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reaction kettle of polytetrafluoroethylene and reacted at 150℃for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol and dried under vacuum to give crystals 0.365 g, 78% yield (as Na 2 MoO 4 Calculation). Elemental analysis: c7.56, H2.43, n 8.79%; theoretical value of element content: C7.69,H 2.58,N 8.97%. Infrared absorption spectrum data (KBr, cm) -1 ): 3299 (w), 3212 (w), 3100 (m), 2916 (w), 2869 (w), 2351 (w), 2023 (w), 1576(s), 1447 (m), 1301 (w), 1252 (w), 1155 (w), 1086 (m), 1010 (m), 941(s), 897 (m), 816 (w), 666 (w), 558 (m), 462 (w). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.55eV。
Embodiment III: [ Ni (en) 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2
NiCl is added 2 ·6H 2 O (0.119 g, 0.5 mmol), na 2 MoO 4 (0.206 g, 1.0 mmol) and Se (0.237 g, 4.0 mmol) were added to 3 ml of ethylenediamine (en) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reaction kettle of polytetrafluoroethylene and reacted at 150℃for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol, and dried under vacuum to give crystals 0.374 g in 80% yield (as Na 2 MoO 4 Calculation). Elemental analysis: c7.51, H2.45, n 8.75%; theoretical value of element content: C7.69,H 2.58,N 8.97%. Infrared absorption spectrum data (KBr, cm) -1 ): 3444 (w), 3207 (m), 3123(s), 2906 (m), 2856 (m), 2362 (w), 2095 (w), 1576(s), 1448 (m), 1379 (w), 1315 (m), 1280 (w), 1117 (m), 1072(s), 994(s), 959 (m), 880 (w), 692 (w), 583 (w), 498 (m). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.57eV。
Embodiment four: [ Mn (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2
MnCl is added to 2 h4H 2 O (0.099 g, 0.5 mmol), na 2 MoO 4 (0.206 g, 1.0 mmol) and Se (0.237 g, 4.0 mmol) were added to 3 ml of a diethylenetriamine (dien) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reaction vessel of polytetrafluoroethylene and reacted at 150℃for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol, and dried under vacuum to give crystals 0.369 g in 77% yield (as Na 2 MoO 4 Calculation). Elemental analysis: c9.85, H2.58, n 8.59%; theoretical value of element content: C10.02,H 2.73,N 8.76%. Infrared absorption spectrum data (KBr, cm) -1 ): 3352 (m), 2939 (m), 2868 (w), 2131 (w), 1630 (m), 1580 (m), 1467(s), 1371(s), 1296(s), 1145 (m), 1042 (m), 968 (w), 914 (w), 811 (m), 731 (m), 601 (m), 574 (m), 504 (w). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.63eV。
Fifth embodiment: [ Co (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2
C is l at the temperature of 2 ·6H 2 O (0.119 g, 0.5 mmol), na 2 MoO 4 (0.206 g, 1.0 mmol) and Se (0.237 g, 4.0 mmol) were added to 3 ml of ethylenediamine (en) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reaction kettle of polytetrafluoroethylene and reacted at 150℃for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol, and dried under vacuum to give crystals 0.390 g in 81% yield (as Na 2 MoO 4 Calculation). Elemental analysis: c9.86, H2.65, n 8.55%; theoretical value of element content: C9.98,H 2.72,N 8.73%. Infrared absorption spectrum data (KBr, cm) -1 ): 3443 (m), 3299(s), 3237(s), 2935 (m), 2880 (m), 2362 (w), 2036 (w), 1567 (m), 1453(s), 1392(s), 1320 (m), 1271 (w), 1083 (m), 1004(s), 974(s), 614 (m), 589 (m), 454 (m). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.58eV。
Example six: [ Ni (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2
NiCl is added 2 ·6H 2 O (0.119 g, 0.5 mmol), na 2 MoO 4 (0.206 g, 1.0 mmol) and Se (0.237)Gram, 4.0 mmol) was added to 3 ml of ethylenediamine (en) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reaction kettle of polytetrafluoroethylene and reacted at 150℃for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol, and dried under vacuum to give crystals 0.404 g in 84% yield (as Na 2 MoO 4 Calculation). Elemental analysis: c9.81, H2.62, n 8.57%; theoretical value of element content: C9.98,H 2.72,N 8.73%. Infrared absorption spectrum data (KBr, cm) -1 ): 3408 (m), 3177(s), 3103(s), 2915 (m), 2875 (m), 1577(s), 1458 (m), 1311 (m), 1142 (w), 1084 (w), 1028(s), 945 (m), 874 (w), 806 (w), 766 (w), 618 (w), 553 (w), 481 (w). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.53eV。
Performance testing
The molybdenum selenium cluster compound containing the transition metal complex ion obtained in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment, the fifth embodiment and the sixth embodiment is used for carrying out photocatalytic degradation on the organic dyes CV and MB. The experimental results are shown in Table 1.
Degradation experiment process: and adding a certain amount of molybdenum selenium cluster compound containing transition metal complex ions into the organic dye solution, irradiating the organic dye solution with Xe light source under continuous stirring, taking a small amount of solution at certain intervals, measuring the visible-ultraviolet absorption spectrum of the solution, detecting the concentration change of CV and MB according to the intensity of the maximum absorption peaks of CV and MB, and further calculating the degradation percentage of CV and MB.
TABLE 1
Therefore, the molybdenum selenium cluster compound containing the transition metal complex ion has good catalytic activity on photodegradation organic dye.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A molybdenum selenium cluster compound containing transition metal complex ions is characterized in that the molybdenum selenium cluster compound has a structural general formula: [ M (en) 3 ]Mo 2 O 2 Se 2 (Se 2 ) 2 Or [ M (dien) 2 ]Mo 2 O 2 Se 2 (Se 2 ) 2 M is Mn, co or Ni; en is ethylenediamine and dien is diethylenetriamine.
2. The preparation method of the molybdenum selenium cluster compound containing the transition metal complex ion is characterized by comprising the following steps: mixing and stirring M-containing salt, a molybdenum source and a selenium source in an ethylene polyamine solvent, and heating for reaction to obtain a molybdenum selenium cluster compound containing transition metal complex ions; m in the M-containing salt is Mn, co or Ni.
3. The method of claim 2, wherein the M-containing salt is selected from MnCl 2 、CoCl 2 And NiCl 2 One or more of the following.
4. The method of claim 2, wherein the molybdenum source is selected from Na 2 MoO 4 And/or MoO 3 。
5. The method of claim 2, wherein the selenium source is selected from Se and/or Na 2 Se。
6. The process according to claim 2, wherein the ethylene polyamine solvent is selected from ethylenediamine and/or diethylenetriamine.
7. The method according to claim 2, wherein the molar ratio of the M-containing salt, the molybdenum source, and the selenium source is 1:2:6 to 1:2:8.
8. The method of claim 2, wherein the heating reaction conditions are: the reaction temperature is 150-180 ℃ and the reaction time is 4-5 days.
9. The method of claim 2, further comprising the step of purifying the molybdenum selenium cluster compound containing the transition metal complex ion by: and after heating, cooling to room temperature, filtering to obtain a filter cake, and washing the filter cake with a detergent to obtain the molybdenum selenium cluster compound containing the transition metal complex ions.
10. Use of the molybdenum selenium cluster compound containing transition metal complex ions as defined in claim 1 or the molybdenum selenium cluster compound containing transition metal complex ions as defined in any one of claims 2-9 in catalyzing photodegradation of organic dyes.
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