A Mo-As-Se ternary selenide containing transition metal ions and its solvothermal preparation method and application

Abstract

The present invention relates to a Mo-As-Se ternary selenide containing a transition metal complex ion and a solvothermal preparation method and application thereof. The Mo-As-Se ternary selenide of the present invention has a general structural formula of: [M(en)3]2Mo2O2Se2(AsSe3)2·en or [M(dien)2]2Mo2O2Se2(AsSe3)2; wherein M is Mn, Co or Ni, en is ethylenediamine, and dien is diethylenetriamine. The synthesis method of the present invention is simple to operate, and uses simple and readily available raw materials to synthesize the Mo-As-Se ternary selenide containing a transition metal complex ion by a one-step reaction, thereby improving the product yield.

Description

Technical Field

[0001] The invention relates to the technical field of selenide materials, in particular to a Mo-As-Se ternary selenide containing transition metal coordination ions and a solvothermal preparation method and application thereof. Background Art

[0002] Transition metals have an unfilled (n-1)d electron layer structure and exhibit good magnetic and luminescent properties, while the multinary metal sulfide compounds of P-block elements antimony (Sb) and arsenic (As) have good semiconductor properties. Therefore, multinary metal sulfide compounds containing transition metals Sb and As are multifunctional composite materials with excellent performance, and their energy gap can be adjusted by selecting different transition metals. They have broad application prospects in the fields of magnetic materials, semiconductor materials, and luminescent and catalytic composite materials. Therefore, the research on multinary metal sulfide compounds containing transition metals Sb and As has attracted widespread attention. For example, Fe-Sb-S ternary antimony sulfide [Fe(tren)]FeSbS4 (tren = tris(2-aminoethyl)amine), [Fe(dien)2]Fe2Sb4S 10 (dien = diethylenetriamine) and [Fe(en)2]Sb4S7 (en = ethylenediamine), as well as Mn-Sb-S ternary sulfide (dienH3) [(dienH)MnSb8S 15 ]·H2O is a magnetic material with good performance; Ag-Sb-S ternary sulfide [NH4]AgSb4S7·H2O and [NH4]AgSb2S4 have strong catalytic effect on the photodegradation of crystal violet; Cu-Sb-Se ternary selenide CuSbSe3·0.5en and CuSbSe3·en are potential semiconductor materials with narrow energy gap, and their energy gaps are 1.58ev and 1.61ev respectively. Mn-As-S ternary arsenic sulfide [NH4]MnAs3S6 is a magnetic material with weak antiferromagnetism, and the magnetism of {[Mn(phen)3](AsS3)2}·H2O (phen=1,10-phenanthroline) has spin-oblique control characteristics. The semiconductor energy gap of Mn-As-Se ternary selenide [Mn(phen)2]As2Se3(Se2) is 2eV, and it has antiferromagnetic interaction.

[0003] Molybdenum (Mo) and arsenic (As) are typical sulfophilic elements that can form Mo-E and As-E (E = O, S, Se) binary sulfides with diverse structures and stable compositions. At present, a series of Mo-S and As-S binary sulfides have been synthesized and characterized, for example, molybdenum sulfur compounds containing organic cations [(CH3)4N]2[Mo2O2(μ-S)2(S2)2], [(CH3)4N]2[Mo2O2(μ-S)2(S2)(S4)], [(CH3)4N]2[Mo2O2(μ-S)2(S2)(S4)]·CH3CN and [Ph4P]2[Mo2O2(μ-S)2(S2)2], and molybdenum sulfur compounds containing organic ligands [Mo2O2(μ-S)2(DMF)3]

[17] 、Mo2O2(μ-S)2(Et2dtc)2(dtc=dithiocarbamate). As-S binary sulfides include Tl3AsS3、[Mn(dien)2] n [Mn(dien)AsS4] 2n ·4nH2O, [Mn(en)3]2[Mn(en)2AsS4][As3S6], [Mn3(2,2'-bipy)3(AsS4)2] n nH2O (2,2'-bipy=2,2'-bipyridine) and [Mn3(phen)3(AsS4)2] n nH2O, etc. There are also some reports on the research of Mo-Se and As-Se binary selenides, but there is no report on Mo-As-Se ternary selenides containing transition metal ions.

[0004] 1. Report on Mo-Se binary selenide

[0005] (1) In 1990, Henkel used (NH4)6Mo7O 24 ·6H2O and NaHSe were used as molybdenum and selenium sources, and Cys (Cys = L(+)-cysteine) was used as an organic ligand to prepare the molybdenum selenium compound Na[(CH3)4N][Mo2O2(μ-Se)2(Cys)2]·7H2O. Due to the multi-step reaction synthesis, the yield was low, only 33%. (See: G. Henkel, G. Kampmann, B. Krebs, GJ Lamprecht, M. Nasreldin, AG Sykes, J. Chem. Soc., Chem. Commun., 1990, 15, 1014-1016.).

[0006] (2) In 1992, Kanatzidis used Mo, K2Se4, and H2O in a molar ratio of 1:1.5:22.2 to react at 135°C for 3 days, cooled to room temperature, and then washed with ethanol to obtain the molybdenum selenide compound K2Mo3Se 18 The yield was 20%; MoO3, K2Se4, and H2O were reacted at the same temperature for 3 days in a molar ratio of 1:2:22.2, and the product was washed with ethanol to obtain a molybdenum selenium compound K8Mo9Se 40 ·4H2O, the yield is about 20%. In 1995, Kanatzidis used MoO3, K2Se4, Me4NCl in a molar ratio of 1:3:2 at 135℃ for 3 days, cooled to room temperature and washed with DMF to remove Se x 2- and NaCl impurities to obtain the molybdenum selenide compound (Me4N)2Mo3Se containing organic cations 13 The above synthetic operations 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).

[0007] (3) In 1993, Eichhorn first reacted Mo2(O2CCH3)4 (O2CCH3 is acetate) and K2Se4 in ethylenediamine for 3 hours, filtered to obtain a clear solution, and then added crown ether 2,2,2-crypt (2,2,2-crypt = 1,4,7,10,13,16-hexaoxacyclooctadecane) to the filtrate. After the reaction was completed, the filtrate was filtered and the filtrate was allowed to stand for 6 days to obtain black crystals [K(2,2,2-crypt)]2[Mo2O2(μ-Se)2(Se2)] with a yield of 55%. The synthetic raw material K2Se4 was prepared by reacting potassium and selenium in liquid ammonia under nitrogen atmosphere. The DMSO and DMF solvents used in the synthesis should be free of water and should be dried over molecular sieves before use and then distilled. (See: BWEichborn, JRGardner, ANZiebah, KJAhmetI, SGBott, Inorg. Chem., 1993, 32, 5412-5414.).

[0008] (4) In 1996, Mak first reacted Mo(CO)6 and K2Se4 in ethanol at 100°C for 72 hours to obtain a black powder. He then reacted the black powder with Et4NCl·H2O in ethanol to prepare the molybdenum selenide compound (Et4N)2[(Mo2O2Se6) 0.20 ((Mo2O2Se6) 0.18 (Mo2O2Se6)0.62 In 1997, Mak mixed Mo(CO)6, Et4NCl·H2O, Ag, and K2Se4 in ethanol, transferred the mixture into a glass tube, cooled it with liquid ammonia, sealed the glass tube, reacted it at 100°C for 72 hours, and then cooled it to 50°C at a rate of 6°C per hour to obtain the molybdenum selenide compound [Et4N]6Mo6Se 42 , with a yield of 5%. The preparation of this compound requires two steps of reaction, with a low yield, and highly toxic Mo(CO)6 must be used as a molybdenum source. The synthetic raw material K2Se4 is prepared under harsh conditions. The preparation method is: under the protection of a nitrogen atmosphere, potassium and selenium in a stoichiometric ratio are reacted in an autoclave at 400°C for 5 hours to obtain K2Se4. (See: GCGuo, TCWMak, Inorg.Chem., 1998, 37, 6538-6540; GCGuo, TCWMak, Dalton Trans. 1997, 709–710.).

[0009] (5) In 2006, Nguyen used MoCl5 and ( i Pr2PSe)2Se( i Pr = isopropyl) was reacted in ethanol for 1 hour to generate a yellow precipitate. After washing the precipitate with ethanol, it was recrystallized in dichloromethane to obtain brown crystals [Mo2O2(μ-Se)2(Se2P i Pr2)2]. Selenium source ( i Pr2PSe)2Se is composed of NEt3, i Pr2PCl, HSiCl3, Se are used as raw materials, through two-step reaction in hexane solvent and toluene solvent, and finally recrystallized in toluene. [Mo2O2(μ-Se)2( i Pr2PSe2)2] and ( i The synthesis of Pr2PSe)2Se requires an inert environment and is performed in a standard Schlenk anhydrous and oxygen-free double-row tube operating system (see: CQ Nguyen, A. Adeogun, M. Afzaal, MA Malik, PO Brien, Chem. Commun., 2006, 20, 2182-2184; CQ Nguyen, A. Adeogun, M. Afzaal, MA Malik, PO Brien, Chem. Commun., 2006, 20, 2179-2181.).

[0010] (6) In 2022, Elliott used a multi-step reaction method to prepare (CH3)4N under nitrogen protection. +A certain amount of selenium powder is added to water, nitrogen is introduced into the water to remove oxygen in the water (i.e. degassing), then NaBH4 is added, and degassing with nitrogen is continued, and the reaction is carried out at 50°C for 40 minutes. Then, ammonium heptamolybdate (NH4)6Mo7O is added 24 , stirred overnight under nitrogen flow and filtered. Tetramethylammonium chloride (CH3)4NCl was added to the filtrate to generate a dark brown precipitate, which was washed with cold water, cold ethanol and ether respectively. The precipitate was dissolved in DMF to form a saturated solution. After the saturated solution was left to stand for several weeks, brown-black crystals [(CH3)4N]2[Mo2O2(μ-Se)2(Se2)2] were precipitated. 24 , Se and Na2Se2 were used instead of selenium powder, and the same synthesis method was used, and finally recrystallized in acetonitrile / ether mixed solvent to prepare [(CH3)4N]2[Mo2O2(μ-Se)2(Se2)(Se4)] 0.5 [Mo2O2(μ-Se)2(Se2)(Se3)] 0.25 [Mo2O2(μ-Se)2(Se2)] 0.25 . (See: A. Elliott, J. McAllister, L. Masaityte, MS Centellas, DLLong, AYGanin, YFSong, C. Bo, HNMiras, Chem. Commun., 2022, 58, 6906-6909.).

[0011] 2. Reports on As-Se binary selenides

[0012] (1) In 1995, Kolis prepared arsenic selenide compounds containing CO ligands through multi-step reactions. As4Se4 was added to DMF, stirred for 12 hours, then Fe(CO)5 was added, and continued to stir at 100°C for 12 hours. Then PPh4Br was added and stirred for another hour. After filtering, the mixture was chromatographed with distilled ether. The chromatographic solution was allowed to stand at 4°C for 12 hours to obtain the compound (PPh4)2[Fe(As3Se3)2(CO)] with a yield of 44%. Mn2(CO) 10 Substituting Fe(CO)5, the same method was used to obtain mixed (PPh4)2[Mn(As3Se5)(CO)3] with a yield of 33%. The above experimental process was carried out in a standard Schlenk anhydrous and oxygen-free (in argon) double-row tube operating system. (See: TMMartin, PTWood, GL Schimek, WTPennington, JW Kolis, Inorg.Chem., 1995, 34, 4385–4391).

[0013] (2) In 1998, Müller used As2Se3, PPh4Br and Na2Se in CH3CN at 60℃ for 24 hours, filtered, and the filtrate was crystallized at -20℃ to obtain Se5 2- The arsenic selenide compound PPh4[AsSe(Se5)] is obtained by increasing the amount of CH3CN, and the arsenic selenide compound (PPh4)2[As2Se6]·2CH3CN is obtained. The above synthesis process needs to be carried out in an air-tight atmosphere. (See: JW Czado, U. Müller, Z. Anorg. Allg. Chem., 1998, 624, 239-243.).

[0014] (3) In 1998, Ibers used AsSe4 in ethylenediamine (en) to ultrasonicate for 8 hours at 60°C, and the resulting red solution was chromatographed with an en solution containing NEt4Br and toluene to obtain (NEt4)2[As2Se6] and (NEt4)[AsSe8]. Due to the multiple steps of reaction and separation, the yields were low, with (NEt4)2[As2Se6] and (NEt4)[AsSe8] yields of 59% and 22%, respectively. TlAsSe4 was ultrasonicated in ethylenediamine (en) at 60°C for 12 hours, and an en solution containing the crown ether 2,2,2-crypt (2,2,2-crypt = 1,4,7,10,13,16-hexaoxacyclooctadecane) was added, and then chromatographed with toluene. After evaporating the toluene, CH3CN was added, and further chromatographed with ether to obtain (enH)[AsSe6]·2,2,2-crypt with a yield of 18%. The experimental raw materials AsSe4 and TlAsSe4 are prepared by the reaction of As, Tl and Se at high temperature in a N2 atmosphere; the solvents used in the experiment, such as en, CH3CN, toluene, and ether, must be dried and the water removed by distillation. (See: DM Smith, MAPell, JA Ibers, Inorg. Chem., 1998, 37, 2340–2343).

[0015] 3. Report on Mo-As-Se ternary selenide

[0016] (1) In 1991, Kolis added As4Se4 and (C4H9)4N]2[MoSe4] to DMF, stirred for 24 hours and filtered. The filtrate was distilled under reduced pressure to remove the solvent DMF, then CH2Cl2 was added and chromatographed with distilled ether. The chromatographic solution was left to stand at 4°C for 12 hours to obtain the Mo-As-Se ternary selenide [(C4H9)4N]2[MoAs2Se 10], with a yield of 10%. The experimental raw material As4Se4 was prepared by ultrasonic reaction of As and Se at 600°C for 16 hours in a N2 atmosphere; the above experimental process was carried out in a standard Schlenk anhydrous and oxygen-free (in argon) double-row tube operating system. (See: S.C. O'neal, W.T. Pennington, J.W. Kolis, J.Am.Chem.Soc.1991,113,710-712.).

[0017] (2) In 1992, Kolis added As4Se4 to DMF, stirred for 4 hours and filtered. Mo(CO)6 was added to the filtrate, stirred for 1 hour, and then (C4H9)4NBr was added. The mixture was heated to 100°C and stirred for 8 hours before filtering. The filtrate was subjected to vacuum distillation to remove the DMF solvent. CH2Cl2 solvent was then added and chromatographed with distilled ether. The chromatographic solution was allowed to stand at 4°C for 12 hours to obtain Mo-As-Se ternary selenide [(C4H9)4N]2[Mo(CO)2(As3Se3)2] containing organic cations with a yield of 20%. As4Se4 and K2Se3 were added to DMF, stirred for 4 hours and filtered. Mo(CO)6 and (C4H9)4NBr were added to the filtrate, heated to 100°C and stirred for 2 hours and filtered. The filtrate was subjected to reduced pressure distillation to remove the solvent DMF, and then CH2Cl2 solvent was added and chromatographed with distilled ether. The chromatographic solution was allowed to stand at 4°C for 12 hours to obtain Mo-As-Se ternary selenide [(C4H9)4N]2[Mo(AsSe5)2] containing organic cations, with a yield of 40%. The entire experimental process was carried out in a standard Schlenk anhydrous and oxygen-free (in argon) double-row tube operating system. The experimental raw material As4Se4 was prepared by ultrasonic reaction of As and Se at 600°C for 16 hours in a N2 gas atmosphere, and K2Se3 was prepared by reaction of K and Se in liquid ammonia at -78°C for 3 hours. (See: S. C. O'neal, WT Pennington, J. W. Kolis, Inorg. Chem., 1992, 31, 888-894).

[0018] In summary, although many Mo-Se and As-Se binary selenides have been synthesized and characterized, only three Mo-As-Se ternary selenides have been reported internationally, and the counter cations of these three Mo-As-Se ternary selenides are all organic cations (C4H9)4N +There are no reports of Mo-As-Se ternary selenides containing transition metal ions in the literature at home and abroad. The preparation of the above-mentioned Mo-As-Se ternary selenides and Mo-Se and As-Se binary selenides requires multi-step reactions. The experimental principle requires preparation under special conditions, requires the use of a large amount of organic solvents, and needs to be carried out in an anhydrous and oxygen-free environment.

[0019] At present, the existing technologies for preparing Mo-As-Se ternary selenides and Mo-Se and As-Se binary selenides are: (1) an anhydrous and oxygen-free operating system is required, and the experiment is usually carried out under nitrogen or argon protection to ensure isolation from air. (2) Mo(CO)6, (NH4)6Mo7O 24 , MoCl5, As4Se4, K2Se4, K2Se3, Na2Se2, ( i Pr2PSe)2Se and other compounds are used as synthetic intermediates. These intermediates are used as molybdenum sources, arsenic sources and selenium sources for synthesizing the target products. The preparation of these intermediates needs to be carried out under harsh conditions such as anhydrous and oxygen-free inert or high temperature. For example, Mo(CO)6, As4Se4, K2Se3, and ( i The preparation of Pr2PSe)2Se was completed under the protection of N2 gas, and the preparation of K2Se4 and Na2Se2 was obtained by reacting at 400℃ for 5 hours in a nitrogen atmosphere; As4Se4 was prepared by ultrasonically reacting As and Se at 400℃ and 600℃ for 16 hours in a N2 atmosphere, which increased the preparation cost. The potassium and sodium required for the preparation of K2Se4, K2Se3, and Na2Se2 are flammable and explosive, and As4Se4 and Mo(CO)6 are highly toxic substances, which increase the experimental safety. (3) The preparation requires multiple steps, including two or more steps, including raw material preparation, repeated extraction, chromatography, precipitation, crystallization and recrystallization. The reaction or operation steps, due to the large number of synthesis steps, result in a low product yield, such as [(C4H9)4N]2[MoAs2Se 10 ] has a yield of 10%; [(C4H9)4N]2[Mo(CO)2(As3Se3)2] has a yield of 20%; [(C4H9)4N]2[Mo(AsSe5)2] has a yield of 40%; [Et4N]6Mo6Se 42 The yield is only 5%; (enH)[AsSe6]·2,2,2-crypt, the yield is 18%. (4) The preparation process is usually carried out in volatile organic solvents such as DMF (N,N-dimethylformamide), CH3CN (acetonitrile), ether, toluene, dichloromethane, etc., and requires multiple steps of repeated extraction, chromatography, precipitation, crystallization and recrystallization with organic solvents. It can be seen that the amount of organic solvents used is large, and these solvents are usually distilled and dehydrated before use, which consumes energy and is not conducive to environmental protection.

[0020] At present, the Mo-As-Se ternary selenides prepared and studied are based on organic cations as counter cations. There are no reports in the literature on the research of Mo-As-Se ternary selenides containing transition metal complex ions, and there are no reports in the literature on the research of preparing Mo-As-Se ternary selenides by one-step reaction. Summary of the invention

[0021] In order to solve the above technical problems, the present invention discloses a preparation method and structure of Mo-As-Se ternary selenide containing transition metal ions by using ethylene polyamine as solvent and ligand.

[0022] The preparation method of the present invention utilizes the chelating coordination effect of ethylene polyamine to synthesize the Mo-As-Se ternary selenide containing transition metal complex ions through a one-step reaction under solvent thermal conditions. The synthesis method is simple to operate, and simple sodium molybdate (Na2MoO4), sodium arsenate (Na3AsO4) and selenium powder are used as molybdenum source, arsenic source and selenium source respectively, avoiding the need to prepare special molybdenum, arsenic and selenium compounds as molybdenum source, arsenic source and selenium source under anhydrous and oxygen-free conditions in the traditional method. The Mo-As-Se ternary selenide containing transition metal complex ions is synthesized by a one-step reaction using simple and readily available raw materials, thereby improving the product yield. The reaction does not need to be carried out under anhydrous and oxygen-free conditions, nor does it need a large amount of organic solvents used in the traditional preparation method. Only two solvents, ethylene polyamine (reaction solvent) and ethanol (washing solvent), are needed, and the solvent does not need to be further dehydrated.

[0023] The first aspect of the present invention aims to overcome the defects of the existing technology for synthesizing Mo-As-Se ternary selenide, which requires multi-step reactions and results in a low final product yield. The multi-step reactions and operations include raw material preparation, repeated extraction, chromatography, precipitation, crystallization and recrystallization.

[0024] The second aspect of the present invention aims to overcome the existing problems in the preparation of Mo-As-Se ternary selenide technology, which requires the synthesis of Mo(CO)6, As4Se4, K2Se4, K2Se3, Na2Se2, ( i The defects of intermediate products such as Pr2PSe)2Se as molybdenum source, arsenic source and selenium source, and the synthesis of these intermediate products needs to be carried out at high temperature above 400℃ (such as K2Se4) and 600℃ (such as As4Se4), or in complex anhydrous and oxygen-free operating systems (such as Mo(CO)6, ( i Pr2PSe)2Se), and use a large amount of volatile organic solvents such as DMF (N,N-dimethylformamide), CH3CN (acetonitrile), ether, toluene, and dichloromethane.

[0025] In order to solve the above technical problems, the present invention is implemented by the following scheme:

[0026] The first object of the present invention is to provide a Mo-As-Se ternary selenide containing a transition metal complex ion, wherein the Mo-As-Se ternary selenide has a general structural formula of: [M(en)3]2Mo2O2Se2(AsSe3)2·en or [M(dien)2]2Mo2O2Se2(AsSe3)2; wherein M is Mn, Co or Ni, en is ethylenediamine, and dien is diethylenetriamine. In the structural formula, [M(en)3] 2+ and [M(dien)2] 2+ Medium 2+ The coordination number is 6, M 2+ The ion is coordinated with 6 N atoms to form an MN6 coordinated octahedron. [Mo2O2Se2(AsSe3)2] 4– By a [Mo2O2(μ-Se)2)] 2+ Double molybdenum core and two arsenic selenium ions AsSe3 3– Composition. Cationic core [Mo2O2(μ-Se)2)] 2+ Two MoO through two μ-Se 2– Each μ-Se 2– The ligand is connected to two Mo atoms at the same time. 3– The ions are bound to the cationic core [Mo2O2(μ-Se)2)] in the form of bidentate chelating ligands. 2+ The two Mo atoms in the ion are coordinated to form the Mo-As-Se ternary anion [Mo2O2Se2(AsSe3)2] 4– .

[0027] The second object of the present invention is to provide a method for preparing a Mo-As-Se ternary selenide containing a transition metal complex ion, comprising the following steps: mixing a salt containing M, a molybdenum source, an arsenic source, and a selenium source in an ethylene polyamine solvent, ultrasonically stirring, and heating for reaction to obtain the Mo-As-Se ternary selenide containing a transition metal complex ion; M in the salt containing M is Mn, Co or Ni.

[0028] In one embodiment of the present invention, the M-containing salt is selected from one or more of MnCl2, CoCl2 and NiCl2.

[0029] In one embodiment of the present invention, the molybdenum source is selected from Na2MoO4 and / or MoO3.

[0030] In one embodiment of the present invention, the arsenic source is selected from Na3AsO4 and / or As.

[0031] In one embodiment of the present invention, the selenium source is selected from Se and / or Na2Se.

[0032] In one embodiment of the present invention, the ethylene polyamine solvent is selected from ethylenediamine and / or diethylenetriamine. Ethylenediamine (boiling point: 116.5°C) and diethylenetriamine (boiling point: 207°C) have high boiling points, are not volatile, are not flammable, avoid environmental pollution, and improve the safety of the preparation process. In the present invention, ethylene polyamine is both a reaction solvent and a chelating agent for transition metal complex ions. It has high polarity and strong solubility, avoids the formation of metal selenide MoSe2, As2Se3, MSe (M=transition metal Mn, Co, Ni) precipitation, is conducive to the crystallization of molybdenum selenium clusters, thereby forming Mo-As-Se ternary selenide crystals, and improving the purity of the product; at the same time, ethylene polyamine has a strong chelating and coordination ability, is easy to form complex ions with transition metal complex ions, and then combines with Mo-As-Se ternary anions to form Mo-As-Se ternary selenide containing transition metal complex ions, ethylene polyamine reacts with transition metal complex ions in situ to form transition metal complex cations, which serve as counter ions of Mo-As-Se ternary selenide, thereby forming Mo-As-Se ternary selenide containing transition metal complex ions. Moreover, ethylene diamine and diethylene triamine do not change the structure of Mo-As-Se ternary anions.

[0033] In one embodiment of the present 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.

[0034] In one embodiment of the present invention, the reaction conditions of the heating reaction are: reaction temperature is 160-180° C., and reaction time is 4-5 days.

[0035] In one embodiment of the present invention, the purification of Mo-As-Se ternary selenide containing transition metal complex ions is also included, and the steps are: 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.

[0036] Furthermore, the detergent is selected from ethanol.

[0037] The third object of the present invention is to provide the use of the Mo-As-Se ternary selenide containing transition metal complex ions in catalytic photodegradation of organic dyes.

[0038] Furthermore, the organic dye includes but is not limited to methylene blue (MB), crystal violet (CV), rhodamine B (RhB), methyl orange (MO) and the like.

[0039] The above technical solution of the present invention has the following advantages compared with the prior art:

[0040] The method for synthesizing the Mo-As-Se ternary selenide containing transition metal complex ions is simple, and a one-pot solvent thermal method is utilized to omit intermediate steps such as raw material preparation, extraction, chromatography, distillation and recrystallization in a traditional synthesis method, and cheap and non-toxic Na2MoO4, Na3AsO4 and Se are used as molybdenum source, arsenic source and selenium source respectively, and the Mo-As-Se ternary selenide containing transition metal complex ions is firstly prepared through a one-step solvent thermal reaction; a large amount of organic solvents in the traditional synthesis method are not used; the product is convenient to separate and purify, and the yield is high; the Mo-As-Se ternary selenide has a clear and stable structure; and the semiconductor energy gap of the Mo-As-Se ternary selenide can be regulated by different transition metal complex ions.

[0041] (1) The present invention uses a one-step solvent thermal reaction to directly synthesize the Mo-As-Se ternary selenide containing transition metal complex ions, thereby reducing the intermediate steps of the synthesis. Compared with the prior art, the synthesis efficiency and product yield are improved, and the yield of the Mo-As-Se ternary selenide containing transition metal complex ions is more than 67%.

[0042] (2) Using cheap and non-toxic Na2MoO4, Na3AsO4 and Se as molybdenum sources, arsenic sources and selenium sources, there is no need to synthesize specific molybdenum, arsenic and selenium compounds as intermediates, thus reducing energy consumption.

[0043] (3) No volatile or flammable organic solvents are used, thus avoiding environmental pollution; no highly toxic, flammable or explosive chemicals such as As4Se4, Mo(CO)6 and metallic potassium are used, thus improving the safety of the experiment of synthesizing and preparing Mo-As-Se ternary selenide.

[0044] (4) The energy gap and semiconductor properties of Mo-As-Se ternary selenide semiconductors can be regulated by different transition metal ligands.

[0045] (5) No organic solvent other than ethylenediamine (EN), diethylenetriamine (DIEN) and ethanol is used. Ethylenediamine, diethylenetriamine and ethanol do not require any pretreatment including distillation to remove water before use. The entire process of preparing Mo-As-Se ternary selenide containing transition metal complex ions does not need to be carried out under anhydrous and oxygen-free inert conditions.

[0046] (6) The Mo-As-Se ternary selenide containing transition metal ions of the present invention has catalytic activity for photodegradation of organic dyes, and the catalytic degradation rate of organic dyes such as methylene blue (MB) and crystal violet (CV) reaches more than 92%.

[0047] (7) To accumulate theoretical and practical experience for the design and synthesis of new Mo-As-Se ternary selenides. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein

[0049] Figure 1 It is a schematic diagram of the preparation process of [M(en)3]2Mo2O2Se2(AsSe3)2·en and [M(dien)2]2Mo2O2Se2(AsSe3)2 of the present invention.

[0050] Figure 2 [Ni(en)3]2Mo2O2Se2(AsSe3)2·en in the present invention 2+ Ion structure diagram.

[0051] Figure 3 [Ni(dien)2]2Mo2O2Se2(AsSe3)2 of the present invention 2+ Ion structure diagram.

[0052] Figure 4 The present invention [Mo2O2Se2(AsSe3)2] 4- Cluster anion structure diagram. DETAILED DESCRIPTION

[0053] The present invention is further described below in conjunction with specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0054] Example 1: [Mn(en)3]2Mo2O2Se2(AsSe3)2·en

[0055] MnCl2·4H2O (0.099 g, 0.5 mmol), Na2MoO4 (0.103 g, 0.5 mmol), Na3AsO4 (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 reactor with polytetrafluoroethylene and reacted at 160°C for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed twice with 5 ml of ethanol, and vacuum dried to obtain 0.265 g of crystals with a yield of 69% (calculated based on Na2MoO4). Elemental analysis: C 10.72, H 3.53, N 12.62%; theoretical value of element content: C10.95, H 3.67, 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 spectroscopy determination: semiconductor energy gap E g =1.75eV.

[0056] Example 2: [Co(en)3]2Mo2O2Se2(AsSe3)2·en

[0057] CoCl2·6H2O (0.119 g, 0.5 mmol), Na2MoO4 (0.103 g, 0.5 mmol), Na3AsO4 (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 reactor with polytetrafluoroethylene and reacted at 160°C for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed twice with 5 ml of ethanol, and vacuum dried to obtain 0.259 g of crystals with a yield of 67% (calculated based on Na2MoO4). Elemental analysis: C 10.67, H 3.48, N 12.55%; theoretical value of element content: C10.89, H 3.66, N12.70%. 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 spectroscopy determination: semiconductor energy gap E g =1.74eV.

[0058] Example 3: [Ni(en)3]2Mo2O2Se2(AsSe3)2·en

[0059] NiCl2·6H2O (0.119 g, 0.5 mmol), Na2MoO4 (0.103 g, 0.5 mmol), Na3AsO4 (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 reactor with polytetrafluoroethylene and reacted at 160°C for 5 days. After cooling to room temperature, black crystals were precipitated, filtered, washed twice with 5 ml of ethanol, and vacuum dried to obtain 0.294 g of crystals with a yield of 76% (calculated based on Na2MoO4). Elemental analysis: C 10.70, H 3.55, N 12.51%; theoretical value of element content: C10.89, H 3.66, N12.70%. 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 spectroscopy determination: semiconductor energy gap E g =1.68eV.

[0060] Example 4: [Mn(dien)2]2Mo2O2Se2(AsSe3)2

[0061] MnCl2·4H2O (0.099 g, 0.5 mmol), Na2MoO4 (0.103 g, 0.5 mmol), Na3AsO4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 ml of diethylenetriamine (dien) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reactor with polytetrafluoroethylene and reacted at 160°C for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed twice with 5 ml of ethanol, and vacuum dried to obtain 0.286 g of crystals with a yield of 75% (calculated based on Na2MoO4). Elemental analysis: C 12.36, H 3.34, N 10.75%; theoretical value of element content: C12.51, H3.41, N 10.94%. 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 spectroscopy determination: semiconductor energy gap E g =1.81eV.

[0062] Example 5: [Co(dien)2]2Mo2O2Se2(AsSe3)2

[0063] CoCl2·6H2O (0.119 g, 0.5 mmol), Na2MoO4 (0.103 g, 0.5 mmol), Na3AsO4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 ml of diethylenetriamine (dien) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reactor with polytetrafluoroethylene and reacted at 160°C for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed twice with 5 ml of ethanol, and vacuum dried to obtain 0.291 g of crystals with a yield of 76% (calculated based on Na2MoO4). Elemental analysis: C 12.41, H 3.31, N 10.82%; theoretical value of element content: C12.51, H3.41, N 10.94%. 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 spectroscopy determination: semiconductor energy gap E g =1.72eV.

[0064] Example 6: [Ni(dien)2]2Mo2O2Se2(AsSe3)2

[0065] NiCl2·6H2O (0.119 g, 0.5 mmol), Na2MoO4 (0.103 g, 0.5 mmol), Na3AsO4 (0.104 g, 0.5 mmol) and Se (0.158 g, 2.0 mmol) were added to 4 ml of diethylenetriamine (dien) mixed solution, stirred for 10 minutes, and the mixture was placed in a stainless steel reactor with polytetrafluoroethylene and reacted at 160°C for 5 days. After cooling to room temperature, dark red crystals were precipitated, filtered, washed twice with 5 ml of ethanol, and vacuum dried to obtain 0.272 g of crystals with a yield of 71% (calculated based on Na2MoO4). Elemental analysis: C 12.34, H 3.28, N 10.78%; theoretical value of element content: C12.52, H3.41, N 10.95%. 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 spectroscopy determination: semiconductor energy gap E g =1.79eV.

[0066] Performance Testing

[0067] The Mo-As-Se ternary selenides containing transition metal complex ions obtained in Example 1, Example 3, Example 4, Example 5, and Example 6 were used to photocatalytically degrade organic dyes CV and MB. The experimental results are shown in Table 1.

[0068] The specific experiment is as follows: take a certain amount of Mo-As-Se ternary selenide containing transition metal complex ions, add it to a solution of organic dye, irradiate the organic dye solution with a Xe lamp light source under constant stirring, take a small amount of solution at certain intervals, measure the visible-ultraviolet absorption spectrum of the solution, detect the concentration changes of CV and MB according to the intensity of the maximum absorption peaks of CV and MB, and then calculate the degradation percentage of CV and MB.

[0069] Table 1

[0070]

[0071] It can be seen that the Mo-As-Se ternary selenide containing transition metal ions obtained in the present invention has good catalytic activity for photodegradation of organic dyes.

[0072] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A Mo-As-Se ternary selenide containing transition metal complex ions, characterized in that: The general structural formula of the Mo-As-Se ternary selenide is: [M(en)3]2Mo2O2Se2(AsSe3)2·en or [M(dien)2]2Mo2O2Se2(AsSe3)2; wherein M is Mn, Co or Ni, en is ethylenediamine, and dien is diethylenetriamine.

2. A method for preparing the Mo-As-Se ternary selenide containing transition metal complex ions according to claim 1, characterized in that: The method comprises the following steps: mixing a salt containing M, a molybdenum source, an arsenic source and a selenium source in an ethylene polyamine solvent, performing ultrasonic stirring and heating for reaction to obtain the Mo-As-Se ternary selenide containing transition metal complex ions; wherein M in the salt containing M is Mn, Co or Ni; The molybdenum source is selected from Na2MoO4 and / or MoO3; The arsenic source is selected from Na3AsO4 and / or As; The selenium source is selected from Se and / or Na2Se; 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; The ethylene polyamine solvent is selected from ethylenediamine or diethylenetriamine; The reaction conditions of the heating reaction are as follows: the reaction temperature is 160-180° C. and the reaction time is 4-5 days.

3. The preparation method according to claim 2, characterized in that: The M-containing salt is selected from one or more of MnCl2, CoCl2 and NiCl2.

4. Use of the Mo-As-Se ternary selenide containing transition metal complex ions as claimed in claim 1 in catalytic photodegradation of organic dyes.

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