CN116621717A - Mo-As-Se ternary selenide containing transition metal complex ions, and solvothermal preparation method and application thereof - Google Patents

Mo-As-Se ternary selenide containing transition metal complex ions, and solvothermal preparation method and application thereof Download PDF

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CN116621717A
CN116621717A CN202310471621.7A CN202310471621A CN116621717A CN 116621717 A CN116621717 A CN 116621717A CN 202310471621 A CN202310471621 A CN 202310471621A CN 116621717 A CN116621717 A CN 116621717A
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贾定先
任陶红
杨肖
张佳华
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Suzhou University
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Abstract

The invention relates to a Mo-As-Se ternary selenide containing transition metal complex ions, and a solvothermal preparation method and application thereof. The structural general formula of the Mo-As-Se ternary selenide is As follows: [ M (en) 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 En or [ M (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is Mn, co or Ni, en is ethylenediamine, dien is diethylenetriamine. The synthesis method of the invention has simple operation and usesSimple and easily obtained raw materials are synthesized into the Mo-As-Se ternary selenide containing transition metal complex ions by one-step reaction, and the product yield is improved.

Description

Mo-As-Se ternary selenide containing transition metal complex ions, and solvothermal preparation method and application thereof
Technical Field
The invention relates to the technical field of selenide materials, in particular to Mo-As-Se ternary selenide containing transition metal complex ions, and a solvothermal preparation method and application thereof.
Background
The transition metal has an unfilled (n-1) d electron layer structure, shows good magnetic property and luminous performance, and the multi-element metal chalcogenides of the elements antimony (Sb) and arsenic (As) in the P region have good semiconductor property, so that the multi-element metal chalcogenides of the Sb and As containing the transition metal are multifunctional composite materials with excellent performance, and the energy gaps of the multi-element metal chalcogenides can be regulated by selecting different transition metals, thereby having wide application prospects in the fields of magnetic materials, semiconductor materials, luminous and catalytic composite materials and the like. Accordingly, research into transition metal-containing Sb and As multi-metal chalcogenides has received great attention. For example, a transition metal ion-containing Fe-Sb-S ternary antimony sulfide [ Fe (tren) ]]FeSbS 4 (tren=tris (2-aminoethyl) amine), [ Fe (dien) 2 ]Fe 2 Sb 4 S 10 (dien=diethylenetriamine) and [ Fe (en) 2 ]Sb 4 S 7 (en=ethylenediamine) and Mn-Sb-S ternary sulfide (diene h) 3 )[(dienH)MnSb 8 S 15 ]·H 2 O is a magnetic material with good performance; ag-Sb-S ternary sulfide [ NH ] 4 ]AgSb 4 S 7 ·H 2 O and [ NH ] 4 ]AgSb 2 S 4 Has strong catalytic action on photodegradation crystal violet; cu-Sb-Se ternary selenide CuSbSe 3 0.5en and CuSbSe 3 En is a potentially semiconductor material with a narrow energy gap of 1.58ev and 1.61ev, respectively. Mn-As-S ternary arsenic sulfide [ NH ] 4 ]MnAs 3 S 6 Is a magnetic material having weak antiferromagnetic properties, and { [ Mn (phen) 3 ](AsS 3 ) 2 }·H 2 The magnetism of O (phen=1, 10-phenanthroline) has spin bias control characteristics. Mn-As-Se ternary selenide [ Mn (phen) ] 2 ]As 2 Se 3 (Se 2 ) Is 2eV and has antiferromagnetic interactions.
Molybdenum (Mo) and arsenic (As) are typical of the sulfur-philic elements, and can form Mo-E and As-philic elements with various structures and stable compositionsE (e=o, S, se) binary chalcogenides. At present, a series of Mo-S and As-S binary sulfides have been synthesized and characterized, for example, molybdenum sulfur compounds [ (CH) containing organic cations 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 compound [ Mo ] containing organic ligand 2 O 2 (μ-S) 2 (DMF) 3 ] [17] 、Mo 2 O 2 (μ-S) 2 (Et 2 dtc) 2 (dtc = dithiocarbamate). As-S binary sulfide has Tl 3 AsS 3 、[Mn(dien) 2 ] n [Mn(dien)AsS 4 ] 2n ·4nH 2 O、[Mn(en) 3 ] 2 [Mn(en) 2 AsS 4 ][As 3 S 6 ]、[Mn 3 (2,2'-bipy) 3 (AsS 4 ) 2 ] n ·nH 2 O (2, 2 '-bipy=2, 2' -bipyridine) and [ Mn 3 (phen) 3 (AsS 4 ) 2 ] n ·nH 2 O, etc. There is also some literature report on the research of Mo-Se and As-Se binary selenides, but no report on Mo-As-Se ternary selenides containing transition metal complex ions is found.
Reports on Mo-Se binary selenides
(1) In 1990, henkel was expressed as (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 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),A.G.Sykes,J.Chem.Soc.,Chem.Commun.,1990,15,1014-1016.)。
(2) In 1992, kanatzidis used Mo, K 2 Se 4 、H 2 O reacts for 3 days at 135 ℃ according to the mol ratio of 1:1.5:22.2, and is washed by ethanol after being cooled to room temperature, thus obtaining molybdenum selenium compound K 2 Mo 3 Se 18 The yield was 20%; moO (MoO) 3 、K 2 Se 4 、H 2 O reacts for 3 days at the same temperature according to the mol ratio of 1:2:22.2, and the product is washed by ethanol to obtain molybdenum selenium compound K 8 Mo 9 Se 40 ·4H 2 O, yield was about 20%. In 1995, kanatzidis used MoO 3 、K 2 Se 4 、Me 4 NCl was reacted at 135℃for 3 days in a molar ratio of 1:3:2, cooled to room temperature and washed with DMF to remove Se x 2- And NaCl impurities to obtain molybdenum selenium compound (Me) containing organic cation 4 N) 2 Mo 3 Se 13 . The above synthetic procedures were all carried out in a glove box under nitrogen atmosphere. (see: J.Liao, M.Kanatzidis, inorg.Chem.,1992,31,431-439; inorg. Chem.,1995,34,2658-2670).
(3) In 1993, eichhorns first used Mo 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, S.G.Bott, inorg.Chem.,1993,32,5412-5414.).
(4) In 1996, mak first used Mo (CO) 6 And K 2 Se 4 Reacting in ethanol at 100deg.C for 72 hr to obtain black powder,then using black powder and Et 4 NCl·H 2 O in ethanol to prepare molybdenum selenium 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 ]. In 1997, mak had Mo (CO) 6 、Et 4 NCl·H 2 O、Ag、K 2 Se 4 Mixing in ethanol, transferring the mixture into glass tube, cooling with liquid ammonia, sealing the glass tube, reacting at 100deg.C for 72 hr, and cooling to 50deg.C at a rate of 6deg.C per hour to obtain molybdenum selenium compound [ Et ] 4 N] 6 Mo 6 Se 42 The yield was 5%. 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, and the preparation method is as follows: under the protection of nitrogen atmosphere, potassium and selenium simple substances with stoichiometric ratio are reacted in an autoclave at 400 ℃ for 5 hours to obtain K 2 Se 4 . (see: G.C.Guo, T.C.W.Mak, inorg.Chem.,1998,37,6538-6540;G.C.Guo,T.C.W.Mak,Dalton Trans.1997,709-710.).
(5) 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 ]. 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.Mali)k,P.O.Brien,Chem.Commun.,2006,20,2182-2184；C.Q.Nguyen,A.Adeogun,M.Afzaal,M.A.Malik,P.O.Brien,Chem.Commun.,2006,20,2179-2181.)。
(6) 2022 Elliott prepared a solution Containing (CH) under nitrogen by a multi-step reaction method 3 ) 4 N + Cationic molybdenum selenium 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, H.N.Miras, chem.Commun.,2022,58,6906-6909.).
Second report on As-Se binary selenide
(1) In 1995, kolis produced arsenic selenium compounds containing CO ligands via a multi-step reaction. Handle As 4 Se 4 DMF was added and after stirring for 12 hours Fe (CO) was added 5 Stirring was continued at 100deg.C for 12 hours, then PPh was added 4 Br, stirring for 1 hr, filtering, and chromatography with distilled diethyl etherThe solution after chromatography was allowed to stand at 4℃for 12 hours to give a compound (PPh) 4 ) 2 [Fe(As 3 Se 3 ) 2 (CO)]The yield was 44%. With Mn 2 (CO) 10 Instead of Fe (CO) 5 In the same manner, a mixture (PPh 4 ) 2 [Mn(As 3 Se 5 )(CO) 3 ]The yield was 33%. The whole experimental process is carried out in a standard Schlenk anhydrous anaerobic (in argon) double-row tube operation system. (see: T.M.Martin, P.T.Wood, G.L.Schimek, W.T.Pennington, J.W.Kolis, inorg.Chem.,1995,34,4385-4391).
(2) In 1998, muller used As 2 Se 3 、PPh 4 Br and Na 2 Se at CH 3 Reacting in CN at 60deg.C for 24 hr, filtering, crystallizing the filtrate at-20deg.C to obtain Se containing polyselenium ion 5 2- Arsenic selenium compound PPh of (C) 4 [AsSe(Se 5 )]Increase CH 3 The amount of CN is used to obtain arsenic selenium compound (PPh) 4 ) 2 [As 2 Se 6 ]·2CH 3 CN, the above synthetic operation needs to be performed in an air-insulated atmosphere. (see J.W. Czado, U.M. Muller, Z.Anorg. Allg. Chem.,1998,624,239-243.).
(3) In 1998, ibers used AsSe 4 Ultrasonic treatment in ethylenediamine (en) at 60deg.C for 8 hr to obtain red solution containing NEt 4 The Br in en solution was chromatographed with toluene to give (NEt 4 ) 2 [As 2 Se 6 ]And (NEt) 4 )[AsSe 8 ]The yield is low due to multi-step reaction and separation, (NEt) 4 ) 2 [As 2 Se 6 ]And (NEt) 4 )[AsSe 8 ]The yields were 59% and 22%, respectively. By TlAsSe 4 Adding an en solution containing crown ether 2,2-crypt (2, 2-crypt=1, 4,7,10,13, 16-hexaoxa-octadecane) into ethylenediamine (en) at 60deg.C for 12 hr, then subjecting to chromatography with toluene, evaporating to remove toluene, and adding CH 3 CN, further chromatography with diethyl ether gave (enH) [ AsSe ] 6 ]2,2-crypt in 18% yield. Experimental raw Material AsSe 4 、TlAsSe 4 From As, tl and Se at N 2 Reaction at high temperature in gas atmosphereObtaining the product; en, CH used in experiments 3 The solvent such as CN, toluene, diethyl ether, etc. is dried, and distilled to remove water. (see: D.M.Smith, M.A.Pell, J.A.Ibers, inorg.Chem.,1998,37,2340-2343).
Third report on Mo-As-Se ternary selenide
(1) In 1991, kolis et al As 4 Se 4 And (C) 4 H 9 ) 4 N] 2 [MoSe 4 ]Adding DMF, stirring for 24 hr, filtering, vacuum distilling to remove solvent DMF, and adding CH 2 Cl 2 Solvent, using distilled diethyl ether to make chromatography, standing the solution after chromatography at 4 deg.C for 12 hr to obtain Mo-As-Se ternary selenide [ (C) containing organic cation 4 H 9 ) 4 N] 2 [MoAs 2 Se 10 ]The yield was 10%. Experimental raw material As 4 Se 4 From As and Se at N 2 Carrying out ultrasonic reaction at 600 ℃ for 16 hours in the gas atmosphere to obtain the catalyst; the whole experimental process is carried out in a standard Schlenk anhydrous anaerobic (in argon) double-row tube operation system. (see: S.C.O' real, W.T.Pennington, J.W.Kolis, J.Am.Chem.Soc.1991,113,710-712.).
(2) In 1992, kolis et al As 4 Se 4 Adding into DMF, stirring for 4 hr, filtering, and adding Mo (CO) into the filtrate 6 After stirring for 1 hour, then (C) 4 H 9 ) 4 NBr, heated to 100deg.C and stirred for 8 hours, filtered, the filtrate is distilled off under reduced pressure to remove solvent DMF, and CH is then added 2 Cl 2 Solvent, using distilled diethyl ether to make chromatography, standing the solution after chromatography at 4 deg.C for 12 hr to obtain Mo-As-Se ternary selenide [ (C) containing organic cation 4 H 9 ) 4 N] 2 [Mo(CO) 2 (As 3 Se 3 ) 2 ]The yield was 20%. Handle As 4 Se 4 And K 2 Se 3 Adding into DMF, stirring for 4 hr, filtering, and adding Mo (CO) into the filtrate 6 And (C) 4 H 9 ) 4 NBr, heated to 100deg.C and stirred for 2 hours, filtered, the filtrate is distilled off under reduced pressure to remove solvent DMF, and CH is then added 2 Cl 2 Solvent, using distilled diethyl ether to make chromatography, standing the solution after chromatography at 4 deg.C for 12 hr to obtain Mo-As-Se ternary selenide [ (C) containing organic cation 4 H 9 ) 4 N] 2 [Mo(AsSe 5 ) 2 ]The yield was 40%. The whole experimental process is carried out in a standard Schlenk anhydrous anaerobic (in argon) double-row tube operating system. Experimental raw material As 4 Se 4 From As and Se at N 2 Ultrasonic reaction at 600 deg.C for 16 hr in gas atmosphere to obtain K 2 Se 3 Is prepared from K and Se through reaction in liquid ammonia at-78 deg.C for 3 hr. (see: S.C.O' real, W.T.Pennington, J.W.Kolis, inorg.Chem.,1992,31,888-894).
In summary, although a few Mo-Se and As-Se binary selenides have been synthesized and characterized, only three Mo-As-Se ternary selenides are reported internationally, and the counter cations of these three Mo-As-Se ternary selenides are all organic cations (C 4 H 9 ) 4 N + The Mo-As-Se ternary selenide containing transition metal complex ions is not reported in the literature at home and abroad. The preparation of the Mo-As-Se ternary selenide and the preparation of the Mo-Se and As-Se binary selenide all need multi-step reaction, the experimental principle needs to be prepared under special conditions, a large amount of organic solvents are needed, and the preparation needs to be carried out under an anhydrous and anaerobic environment.
At present, the prior art for preparing Mo-As-Se ternary selenide and Mo-Se and As-Se binary selenide comprises the following steps: (1) An anhydrous, anaerobic operating system is required, typically under nitrogen or argon protection to ensure air isolation. (2) Mo (CO) needs to be synthesized first 6 、(NH 4 ) 6 Mo 7 O 24 、MoCl 5 、As 4 Se 4 、K 2 Se 4 、K 2 Se 3 、Na 2 Se 2 、( i Pr 2 PSe) 2 Se and other compounds are used as synthesis intermediates, and the intermediates are respectively used as molybdenum source, arsenic source and selenium source of synthesis target products, and the preparation of the intermediates is required to be carried out under anhydrous and anaerobic inert or high-temperature and other harsh conditions, such as Mo (CO) 6 、As 4 Se 4 、K 2 Se 3 And (3) sum up 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; as As 4 Se 4 From As and Se at N 2 The preparation method is characterized in that the preparation method is prepared by ultrasonic reaction for 16 hours at 400 ℃ and 600 ℃ in gas atmosphere, thus increasing the preparation cost and preparing K 2 Se 4 、K 2 Se 3 、Na 2 Se 2 Potassium and sodium which are required to be used in the process are inflammable and explosive products, as 4 Se 4 And Mo (CO) 6 Are highly toxic substances, which increase experimental unsafe. (3) The preparation requires multiple steps, two or more steps including raw material preparation, repeated extraction, chromatography, precipitation, crystallization, recrystallization, etc. or operation steps, and the synthesis steps are more, which results in lower product yield, such as [ (C) 4 H 9 ) 4 N] 2 [MoAs 2 Se 10 ]The yield was 10%; [ (C) 4 H 9 ) 4 N] 2 [Mo(CO) 2 (As 3 Se 3 ) 2 ]The yield was 20%; [ (C) 4 H 9 ) 4 N] 2 [Mo(AsSe 5 ) 2 ]The yield was 40%; [ Et ] 4 N] 6 Mo 6 Se 42 Yield was only 5%; (enH) [ AsSe 6 ]2,2-crypt in 18% yield. (4) The preparation process is generally carried out in DMF (N, N-dimethylimide), CH 3 The process is carried out in volatile organic solvents such as CN (acetonitrile), diethyl ether, toluene, methylene dichloride and the like, and the process needs to be carried out repeatedly by using the organic solvents in multiple steps such as extraction, chromatography, precipitation, crystallization, recrystallization and the like, so that the use amount of the organic solvents is large, and the solvents usually need to be distilled and the like for water removal treatment before use, so that energy sources are consumed, and the environment protection is also not facilitated.
At present, the Mo-As-Se ternary selenide prepared and researched by people takes organic cations As counter cations, the research of the Mo-As-Se ternary selenide containing transition metal complex ions is not reported in the literature, and the research of preparing the Mo-As-Se ternary selenide by one-step reaction is not reported in the literature.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a preparation method and a structure for synthesizing Mo-As-Se ternary selenide containing transition metal complex ions by taking ethylene polyamine As a solvent and a ligand.
The preparation method of the invention utilizes the chelation coordination effect of ethylene polyamine, synthesizes Mo-As-Se ternary selenide containing transition metal complex ions through one-step reaction under solvothermal condition, has simple operation, and uses simple sodium molybdate (Na 2 MoO 4 ) Sodium arsenate (Na) 3 AsO 4 ) And selenium powder is used As molybdenum source, arsenic source and selenium source, which avoids the need of preparing special molybdenum, arsenic and selenium compounds As intermediate steps of molybdenum source, arsenic source and selenium source under anhydrous and anaerobic condition in the traditional method, and utilizes simple and easily obtained raw materials to synthesize Mo-As-Se ternary selenide containing transition metal complex ions by one-step reaction, thereby improving the product yield. 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 (reaction solvent) and ethanol (washing solvent) are required, and the solvents are not required to be subjected to further water removal treatment.
The first aspect of the invention aims to overcome the defect that the prior Mo-As-Se ternary selenide synthesis technology needs multiple steps of reactions, which lead to lower yield of a final product, wherein the multiple steps of reactions and operations comprise raw material preparation, repeated extraction, chromatography, precipitation, crystallization, recrystallization and the like.
The second aspect of the invention aims to overcome the prior technology for preparing Mo-As-Se ternary selenide to synthesize Mo (CO) 6 、As 4 Se 4 、K 2 Se 4 、K 2 Se 3 、Na 2 Se 2 、( i Pr 2 PSe) 2 Se and other intermediates have the defects of molybdenum source, arsenic source and selenium source, and the synthesis of the intermediates needs to be carried out at 400 ℃ (such as K) 2 Se 4 ) And 600 ℃ (e.g. As) 4 Se 4 ) The above high temperature, or in a complex anhydrous, anaerobic operating system (e.g., mo (CO) 6 、( i Pr 2 PSe) 2 Se)And using a large amount of DMF (N, N-dimethylimide), CH 3 CN (acetonitrile), diethyl ether, toluene, methylene chloride, and the like.
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 Mo-As-Se ternary selenide containing transition metal complex ions, wherein the structural general formula of the Mo-As-Se ternary selenide is As follows: [ M (en) 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 En or [ M (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is Mn, co or Ni, en is ethylenediamine, dien is diethylenetriamine. In the structure [ M (en) ] 3 ] 2+ And [ M (dien) 2 ] 2+ M in (v) 2+ Coordination numbers are all 6, M 2+ The ion coordinates to 6N atoms to form MN 6 Coordination octahedra. [ Mo 2 O 2 Se 2 (AsSe 3 ) 2 ] 4– From one [ Mo ] 2 O 2 (μ-Se) 2 )] 2+ Double molybdenum core and two arsenic selenium ions AsSe 3 3– 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. Two AsSe 3 3– The ion is respectively combined with the cation core [ Mo ] in the form of bidentate chelating ligand 2 O 2 (μ-Se) 2 )] 2+ Two Mo atoms in the catalyst coordinate to finally form Mo-As-Se ternary anions [ Mo ] 2 O 2 Se 2 (AsSe 3 ) 2 ] 4– 。
The second object of the present invention is to provide a method for preparing Mo-As-Se ternary selenide containing transition metal complex ions, comprising the steps of: mixing M-containing salt, a molybdenum source, an arsenic source and a selenium source in an ethylene polyamine solvent, carrying out ultrasonic stirring, and carrying out heating reaction to obtain the Mo-As-Se ternary selenide 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 arsenic source is selected from Na 3 AsO 4 And/or As.
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 boiling points of ethylenediamine (boiling point: 116.5 ℃) and diethylenetriamine (boiling point: 207 ℃) are high, the ethylenediamine is not easy to volatilize and flammable, the environmental pollution is avoided, and meanwhile, the safety of the preparation process is improved. The ethylene polyamine is not only a reaction solvent, but also a chelating ligand of transition metal complex ions, has large polarity and strong solubility, and avoids metal selenide MoSe 2 、As 2 Se 3 The formation of the precipitation of MSe (M=transition metals Mn, co and Ni) is beneficial to the crystallization of molybdenum selenium cluster compound, so that Mo-As-Se ternary selenide crystals are formed, and the purity of the product is improved; meanwhile, the ethylene polyamine has strong chelating coordination capacity, is easy to form complex ions with transition metal complex ions, and is further combined with Mo-As-Se ternary anions to form Mo-As-Se ternary selenide containing the transition metal complex ions, and the ethylene polyamine reacts with the transition metal complex ions in situ to form transition metal complex cations serving As counter ions of the Mo-As-Se ternary selenide, so that the Mo-As-Se ternary selenide containing the transition metal complex ions is formed. And ethylenediamine and diethylenetriamine do not change the structure of Mo-As-Se ternary anions.
In one embodiment of the invention, the molar ratio of the M-containing salt, the molybdenum source, the arsenic source, and the selenium source is 1:1:1:4-1:1:1:5.
In one embodiment of the invention, the reaction conditions of the heating reaction are that the reaction temperature is 160-180 ℃ and the reaction time is 4-5 days.
In one embodiment of the invention, the method further comprises the steps of purifying Mo-As-Se ternary selenide containing transition metal complex ions, wherein the steps are As follows: after heating, cooling to room temperature, filtering to obtain a filter cake, and washing the filter cake with a detergent to obtain the Mo-As-Se ternary selenide containing transition metal complex ions.
Further, the detergent is selected from ethanol.
The third object of the invention is to provide the application of the Mo-As-Se ternary selenide containing transition metal complex ions 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 Mo-As-Se ternary selenide containing transition metal complex ions is simple, utilizes a solvothermal one-pot method, omits intermediate steps of raw material preparation, extraction, chromatography, distillation, recrystallization and the like in the traditional synthesis method, and uses cheap and nontoxic Na 2 MoO 4 、Na 3 AsO 4 And Se are respectively used As a molybdenum source, an arsenic source and a selenium source, and Mo-As-Se ternary selenide containing transition metal complex ions is prepared 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 Mo-As-Se ternary selenide has definite and stable structure; the energy gap of the Mo-As-Se ternary selenide semiconductor can be regulated and controlled through the difference of transition metal complex ions.
(1) The invention uses one-step solvothermal reaction to directly synthesize the Mo-As-Se ternary selenide containing transition metal complex ions, reduces the intermediate steps of synthesis, and improves the synthesis efficiency and the product yield compared with the prior art, wherein the yield of the Mo-As-Se ternary selenide containing transition metal complex ions reaches more than 67 percent.
(2) Using cheap and nontoxic Na 2 MoO 4 、Na 3 AsO 4 And Se is used as a molybdenum source, an arsenic source and a selenium source, and specific compounds of molybdenum, arsenic and selenium are not needed to be synthesized as intermediates, so that the energy consumption is reduced.
(3)、No volatile and inflammable organic solvent is used, thus avoiding environmental pollution; without using As 4 Se 4 、Mo(CO) 6 And highly toxic and flammable explosive medicines such As metallic potassium, and the like, and improves the experimental safety of synthesizing and preparing Mo-As-Se ternary selenide.
(4) The energy capacity and the semiconductor performance of the Mo-As-Se ternary selenide semiconductor can be regulated and controlled through the difference of transition metal complex ions.
(5) 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. The whole process for preparing the Mo-As-Se ternary selenide containing transition metal complex ions does not need to be carried out under an anhydrous and anaerobic inert bar.
(6) The Mo-As-Se ternary selenide containing transition metal complex ions has catalytic activity on photodegradation organic dyes, and the catalytic degradation percentage of the ternary selenide containing transition metal complex ions on the organic dyes such As Methylene Blue (MB) and Crystal Violet (CV) reaches more than 92 percent.
(7) And accumulating theoretical and practical experience for designing and synthesizing novel Mo-As-Se ternary selenide.
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 that are illustrated in the appended drawings, in which
FIG. 1 is a schematic illustration of the invention [ M (en) ] 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 En and [ M (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 Schematic diagram of the preparation process.
FIG. 2 is a drawing of the present invention [ Ni (en) 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 En in [ Ni (en) ] 3 ] 2+ Structure of ion-pairing.
FIG. 3 is a drawing of the present invention [ Ni (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 Middle [ Ni (dien) 2 ] 2+ Structure diagram of ion-complex。
FIG. 4 is a diagram of the present invention [ Mo ] 2 O 2 Se 2 (AsSe 3 ) 2 ] 4- Cluster anion structure diagram.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Embodiment one: [ Mn (en) 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 ·en
MnCl is added to 2 ·4H 2 O (0.099 g, 0.5 mmol), na 2 MoO 4 (0.103 g, 0.5 mmol), na 3 AsO 4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 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 160℃for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol and dried under vacuum to give crystals 0.265 g in 69% yield (as Na 2 MoO 4 Calculation). Elemental analysis: C10.72,H 3.53,N 12.62%; theoretical value of element content: c10.95, H3.67, N12.77%. Infrared absorption spectrum data (KBr, cm) -1 ): 3392 (s), 3256(s), 2955(s), 1610 (m), 1508 (m), 1312 (w), 1086 (w), 991 (w), 939 (w), 760(s), 665 (w), 476 (w). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.75eV。
Embodiment two: [ Co (en) 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 ·en
C oCl 2 ·6H 2 O (0.119 g, 0.5 mmol), na 2 MoO 4 (0.103 g, 0.5 mmol), na 3 AsO 4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 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 160℃for 5 days. Cooling to room temperature, precipitating blackThe crystals were filtered, washed 2 times with 5 ml ethanol and dried under vacuum to give 0.259 g of crystals with 67% yield (as Na 2 MoO 4 Calculation). Elemental analysis: C10.67,H 3.48,N 12.55%; theoretical value of element content: c10.89, H3.66, n 12.70%. Infrared absorption spectrum data (KBr, cm) -1 ): 3410 (s), 3244(s), 3178(s), 2914 (m), 2870 (m), 1578 (m), 1460 (w), 1358 (m), 1335 (w), 1275 (w), 1078 (m), 1009 (w), 959 (w), 887 (w), 592 (w), 505 (w). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.74eV。
Embodiment III: [ Ni (en) 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 ·en
NiCl is added 2 ·6H 2 O (0.119 g, 0.5 mmol), na 2 MoO 4 (0.103 g, 0.5 mmol), na 3 AsO 4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 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 160℃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 0.294 g, 76% yield (as Na 2 MoO 4 Calculation). Elemental analysis: C10.70,H 3.55,N 12.51%; theoretical value of element content: c10.89, H3.66, n 12.70%. Infrared absorption spectrum data (KBr, cm) -1 ): 3450 (w), 3280(s), 3220(s), 2870 (m), 2360 (w), 1580 (m), 1450 (w), 1320 (w), 1060(s), 968(s), 870 (w), 779 (w), 656 (w), 584 (w), 509 (w), 451(s). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.68eV。
Embodiment four: [ Mn (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2
MnCl is added to 2 ·4H 2 O (0.099 g, 0.5 mmol), na 2 MoO 4 (0.103 g, 0.5 mmol), na 3 AsO 4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 ml of diethylenetriamine (dien) mixed solution and stirred for 10 minutes, the mixture was put into a stainless steel counter of polytetrafluoroethyleneThe reaction was carried out in a reaction vessel at 160℃for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol and dried under vacuum to give 0.286 g of crystals with 75% yield (as Na 2 MoO 4 Calculation). Elemental analysis: C12.36,H 3.34,N 10.75%; theoretical value of element content: c12.51, H3.41, N10.94%. Infrared absorption spectrum data (KBr, cm) -1 ): 3440 (w), 3290(s), 3240(s), 2930 (m), 2870 (m), 2090 (w), 1580(s), 1460 (m), 1320 (m), 1070 (m), 1000(s), 949(s), 872 (m), 617 (m), 455(s). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.81eV。
Fifth embodiment: [ Co (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2
CoCl is to be processed 2 ·6H 2 O (0.119 g, 0.5 mmol), na 2 MoO 4 (0.103 g, 0.5 mmol), na 3 AsO 4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 ml of diethylenetriamine (dien) mixed solution and stirred for 10 minutes, and the mixture was placed in a stainless steel reaction vessel of polytetrafluoroethylene and reacted at 160℃for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol and dried under vacuum to give crystals 0.291 g, 76% yield (as Na 2 MoO 4 Calculation). Elemental analysis: C12.41,H 3.31,N 10.82%; theoretical value of element content: c12.51, H3.41, N10.94%. Infrared absorption spectrum data (KBr, cm) -1 ): 3450 (m), 3154(s), 3045(s), 2961(s), 2867(s), 1570(s), 1460(s), 1310 (w), 1110(s), 1070(s), 966(s), 936 (w), 777 (m), 615(s), 521 (m), 436(s). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.72eV。
Example six: [ Ni (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2
NiCl is added 2 ·6H 2 O (0.119 g, 0.5 mmol), na 2 MoO 4 (0.103 g, 0.5 mmol), na 3 AsO 4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 ml of diethylenetriamine (dien) mixed solutionThe mixture was stirred for 10 minutes and placed in a stainless steel reaction vessel of polytetrafluoroethylene and reacted at 160℃for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed 2 times with 5 ml of ethanol and dried under vacuum to give crystals 0.272 g in 71% yield (as Na 2 MoO 4 Calculation). Elemental analysis: C12.34,H 3.28,N 10.78%; theoretical value of element content: c12.52, H3.41, N10.95%. Infrared absorption spectrum data (KBr, cm) -1 ): 3408 (m), 3290(s), 3231(s), 3086(s), 2914 (m), 2874 (m), 1560 (m), 1454 (m), 1379 (w), 1327 (m), 1207 (m), 1165 (m), 1047 (m), 955 (m), 768 (m), 646 (w), 580 (m), 542 (m), 496 (w). Solid state absorption spectrometry: semiconductor energy gap E g ＝1.79eV。
Performance testing
The Mo-As-Se ternary selenide containing the transition metal complex ions obtained in the first embodiment, the third embodiment, the fourth embodiment, the fifth embodiment and the sixth embodiment are subjected to photocatalytic degradation on organic dyes CV and MB. The experimental results are shown in Table 1.
The specific experiment is as follows: adding a certain amount of Mo-As-Se ternary selenide 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 Mo-As-Se ternary selenide containing transition metal complex ions 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. The Mo-As-Se ternary selenide containing transition metal complex ions is characterized by having a structural general formula: [ M (en) 3 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 En or [ M (dien) 2 ] 2 Mo 2 O 2 Se 2 (AsSe 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is Mn, co or Ni, en is ethylenediamine, dien is diethylenetriamine.
2. The preparation method of the Mo-As-Se ternary selenide containing transition metal complex ions is characterized by comprising the following steps of: mixing M-containing salt, a molybdenum source, an arsenic source and a selenium source in an ethylene polyamine solvent, carrying out ultrasonic stirring, and carrying out heating reaction to obtain the Mo-As-Se ternary selenide 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 arsenic source is selected from Na 3 AsO 4 And/or As.
6. The method of claim 2, wherein the selenium source is selected from Se and/or Na 2 Se。
7. The process according to claim 2, wherein the ethylene polyamine solvent is selected from ethylenediamine and/or diethylenetriamine.
8. The method of claim 2, wherein the molar ratio of the M-containing salt, the molybdenum source, the arsenic source, and the selenium source is 1:1:1:4-1:1:1:5.
9. The preparation method according to claim 2, wherein the reaction condition of the heating reaction is that the reaction temperature is 160-180 ℃ and the reaction time is 4-5 days.
10. Use of a Mo-As-Se ternary selenide comprising a transition metal complex ion according to claim 1 or a Mo-As-Se ternary selenide comprising a transition metal complex ion according to any one of claims 2 to 9 for the catalytic photodegradation of organic dyes.
CN202310471621.7A 2023-04-27 2023-04-27 Mo-As-Se ternary selenide containing transition metal complex ions, and solvothermal preparation method and application thereof Pending CN116621717A (en)

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