CN114835760B - Methyl urea nickel-copper complex, crystal material thereof, preparation method and application - Google Patents
Methyl urea nickel-copper complex, crystal material thereof, preparation method and application Download PDFInfo
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- CN114835760B CN114835760B CN202110138869.2A CN202110138869A CN114835760B CN 114835760 B CN114835760 B CN 114835760B CN 202110138869 A CN202110138869 A CN 202110138869A CN 114835760 B CN114835760 B CN 114835760B
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- 239000013078 crystal Substances 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 68
- -1 Methyl urea nickel-copper Chemical compound 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 52
- 230000003287 optical effect Effects 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- 239000002178 crystalline material Substances 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 28
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 19
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 claims description 19
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- LKNLEKUNTUVOML-UHFFFAOYSA-L nickel(2+);sulfate;hydrate Chemical compound O.[Ni+2].[O-]S([O-])(=O)=O LKNLEKUNTUVOML-UHFFFAOYSA-L 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical group O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 10
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000013590 bulk material Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000011365 complex material Substances 0.000 claims 2
- 235000005811 Viola adunca Nutrition 0.000 abstract description 6
- 240000009038 Viola odorata Species 0.000 abstract description 6
- 235000013487 Viola odorata Nutrition 0.000 abstract description 6
- 235000002254 Viola papilionacea Nutrition 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical class [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000411 transmission spectrum Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910002441 CoNi Inorganic materials 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a crystal material of a methylurea nickel-copper complex, a preparation method and application thereof, wherein the crystal material is prepared from M (C) 2 H 6 N 2 O) 6 SO 4 A representation; wherein M represents Ni element and Cu element. The molecular weight of the crystal material is 604.13, and the density is 1.43g/cm 3 F (000) =1902, belonging to the trigonal system, the space group is R-3c, the unit cell parameters areα=90°, β=90°, γ=120°, and unit cell volume ofNumber of molecules in unit cell z=6. The crystal material has good transmission performance on green light, almost fully absorbs blue-violet light and near infrared light, can be used for manufacturing crystal filter devices, is applied to optical devices, and has high practicability.
Description
Technical Field
The invention belongs to the field of transition metal complex crystal materials, and particularly relates to a methylurea nickel-copper complex, a crystal material thereof, a preparation method and application.
Background
In recent years, many researchers have attracted attention to find filters effective for visible light, ultraviolet light, and infrared light. The optical filter can be applied to different filters according to the difference of optical properties of the filters. The types of filters are mainly absorptive filters, dichroic filters, infrared filters, ultraviolet filters, neutral density filters, long wave/short wave filters, polarization filters, and the like.
Currently, researchers' efforts have focused mainly on the synthesis of new optical crystals, which have a broad filtration range. In addition, the crystal material used as the optical filter should also have the conditions of few impurities and defects, good thermal stability, relatively large crystal size and the like so as to meet the specific requirements of different optical filters on optical properties.
NiSO 4 ·6H 2 The O (abbreviated as NSH) crystal has ultraviolet spectrum, which is transparent and filtered to be high>85 percent of the ultraviolet filter material has the excellent characteristics of narrow bandwidth (200-320 nm), absorption of other waves Duan Jiang and the like, and is used as a commercialized ultraviolet filter material with excellent performance. In recent years, research on NSH crystalline materials has not been discontinued, and researchers have synthesized some new crystalline materials by means of ion doping and ligand exchange, and studied their optical properties.
For example, prior art (Zhuang Xinxin. Nickel sulfate series Complex crystal structure, growth and Property Studies [ D)]NH reported by the institute of Structure of substances at Fujian, academy of sciences of China, 2004) 4 ) 2 Ni(SO 4 ) 2 ·6H 2 O、FeNi(SO 4 ) 2 ·12H 2 O、CoNi(SO 4 ) 2 ·12H 2 O、Mn 0.19 Ni 0.81 (SO 4 ) 2 ·7H 2 O、Zn 0.24 Ni 0.76 (SO 4 ) 2 ·7H 2 Synthesis of novel ultraviolet crystal material of O-series nickel sulfate complex by introducing transition metal ion Fe into NSH crystal material 2+ 、Co 2+ 、Mn 2+ 、Zn 2+ Or non-metal ions NH 4 + After that, a series of nickel sulfate crystal materials with good ultraviolet filtering performance are prepared. As another example, the prior art also (Wang Wenting. Research on the growth, structure and properties of the crystal of the hexamethylurea sulfate series [ D ]]University of Fuzhou, 2017.) reports Mn x Ni (1-x) (C 2 H 6 N 2 O) 6 SO 4 、Co 0.5 Ni 0.5 (C 2 H 6 N 2 O) 6 SO 4 Two new crystal materials of nickel sulfate complex are prepared by introducing transition metal ion Mn 2+ 、Co 2+ NSH crystal material with novel spectrum is prepared, and methyl urea molecules with strong coordination ability are utilized to replace coordination molecule water in the crystal, so that the thermal stability of the material is obviously improved.
However, by doping Fe 2+ 、Co 2+ 、Mn 2+ 、Zn 2+ Or non-metal ions NH 4 + And then, the prepared nickel sulfate crystal material has poor permeability to blue-green light and insufficient absorption to near ultraviolet band and near infrared band. Therefore, how to develop a crystalline material with good light transmittance for blue-green light and good filtering performance for strong absorption for near ultraviolet band and near infrared band is a technical problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a methylurea nickel-copper complex which is prepared by using M (C 2 H 6 N 2 O) 6 SO 4 A representation; wherein M represents Ni element and Cu element.
According to an embodiment of the invention, the methylurea nickel copper complex is prepared in Cu x Ni 1-x (C 2 H 6 N 2 O) 6 SO 4 X represents the mole number of Cu element, 0<x<1. Preferably, 0.1.ltoreq.x.ltoreq.0.9; also preferably, 0.3.ltoreq.x.ltoreq.0.8; for example, x=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.66, 0.7, 0.8, 0.9.
According to an embodiment of the invention, the methyl urea nickel copper complex has a molecular weight of 604.13 and a density of 1.43g/cm 3 。
According to an exemplary embodiment of the present invention, the methylurea nickel copper complex is prepared with Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 And (3) representing.
The invention also provides the methyl ureaCrystalline material of nickel copper complex in M (C 2 H 6 N 2 O) 6 SO 4 A representation; wherein M represents Ni element and Cu element.
According to an embodiment of the present invention, the crystalline material is in Cu x Ni 1-x (C 2 H 6 N 2 O) 6 SO 4 X represents the mole number of Cu element, 0<x<1. Preferably, 0.1.ltoreq.x.ltoreq.0.9; also preferably, 0.3.ltoreq.x.ltoreq.0.8; for example, x=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.66, 0.7, 0.8, 0.9.
According to an exemplary embodiment of the present invention, the crystal material is made of Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 And (3) representing. Preferably, the crystal material belongs to a trigonal system, the space group is R-3c, and the unit cell parameter isα=90°, β=90°, γ=120°. According to an embodiment of the invention, the unit cell volume of the crystalline material is +.>
According to an embodiment of the invention, the number of molecules z=6 in the unit cell of the crystalline material.
According to an embodiment of the invention, the crystalline material has a molecular weight of 604.13 and a density of 1.43g/cm 3 ，F(000)＝1902。
According to an embodiment of the invention, the crystalline material has a molecular structure substantially as shown in figure 1.
According to an embodiment of the invention, the crystalline material is a yellowish green transparent bulk material, preferably a millimeter-sized transparent bulk material. Wherein the millimeter scale means that the dimension in at least two dimensions is at least 1mm.
According to an embodiment of the invention, the crystalline material has an X-ray crystal diffraction pattern substantially as shown in figure 6.
According to an embodiment of the invention, the crystalline material has an ultraviolet visible transmission spectrum profile substantially as shown in figure 8.
According to an embodiment of the invention, the transmission spectrum of the crystalline material has a maximum transmission characteristic peak in the wavelength range of 540-560nm, preferably 551 nm. Namely, the crystal material has good transmittance performance for green light in the wavelength range, and the transmittance is higher than 45%.
According to an embodiment of the invention, the crystalline material has a strong absorption of blue-violet light having a wavelength in the range of 405-420nm (the crystalline material has a transmittance of less than 6%, preferably less than 5% for blue-violet light having a wavelength in the range of 405-420 nm), preferably a strong absorption of blue-violet light having a wavelength around 411 nm.
According to an embodiment of the invention, the crystalline material absorbs almost completely ultraviolet light of 200-370nm and near infrared light of 800-1000 nm.
According to an exemplary embodiment of the present invention, the crystal material is made of Cu 0.51 Ni 0.49 (C 2 H 6 N 2 O) 6 SO 4 、Cu 0.32 Ni 0.68 (C 2 H 6 N 2 O) 6 SO 4 Or Cu 0.89 Ni 0.11 (C 2 H 6 N 2 O) 6 SO 4 And (3) representing.
The invention also provides a preparation method of the methyl urea nickel-copper complex and/or the crystal material, which comprises the steps of evaporating solvent of methyl urea, nickel sulfate hydrate and copper sulfate hydrate to react and crystallize through solvent solution, so as to obtain the methyl urea nickel-copper complex and/or the crystal material.
According to an embodiment of the invention, the molar ratio of hydrated sulphate to methyl urea is 1 (5.5-6.5), for example 1:5.5, 1:6, 1:6.5; preferably 1:6;
wherein the molar amount of hydrated sulfate refers to the sum of the molar amounts of copper sulfate hydrate and nickel sulfate hydrate.
According to an embodiment of the invention, the nickel sulphate hydrate may be selected from nickel sulphate hexahydrate and/or nickel sulphate heptahydrate, preferably nickel sulphate hexahydrate.
According to an embodiment of the invention, the copper sulphate hydrate may be selected from copper sulphate pentahydrate and/or copper sulphate monohydrate, preferably copper sulphate pentahydrate.
According to an embodiment of the present invention, the molar ratio of nickel sulfate hydrate to copper sulfate hydrate is x (1-x), 0< x <1. Preferably, 0.1.ltoreq.x.ltoreq.0.9; for example, x=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.66, 0.7, 0.8, 0.9.
For example, the molar ratio of nickel sulfate hydrate to copper sulfate hydrate is 0.1:0.9, 0.2:0.8, 0.3:0.7, 0.4:0.6, 1:1, 0.6:0.4, 0.7:0.3, 0.8:0.2, 0.9:0.1.
According to an embodiment of the present invention, the solvent may be water.
According to an embodiment of the present invention, the methyl urea, nickel sulfate hydrate and copper sulfate hydrate may be mixed in the form of aqueous solutions thereof or added to water before the solvent evaporation reaction. For example, an aqueous solution of methyl urea, an aqueous solution of nickel sulfate hydrate, and an aqueous solution of copper sulfate hydrate are prepared separately, and then the three aqueous solutions are mixed to obtain a mixed solution.
Preferably, the aqueous solution of nickel sulfate hydrate, the aqueous solution of copper sulfate hydrate and the aqueous solution of methyl urea are stirred during preparation to completely dissolve the raw materials. For example, the three aqueous solutions may be filtered separately before the three aqueous solutions are mixed. For another example, the three solutions may be mixed first and then the mixed solution may be filtered.
For example, the filtration may be performed by using a microporous membrane, preferably a membrane having a pore size of 0.05 to 1. Mu.m.
According to an embodiment of the invention, the mixed solution is a clear solution; for example, heating may be performed during the mixing of the three aqueous solutions to obtain a clear mixed solution; alternatively, the three solutions may be mixed and then heated to obtain a clear mixed solution.
Preferably, the temperature of the heating is 30-70 ℃, preferably 50-70 ℃, and exemplary is 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃.
According to an embodiment of the present invention, the pH of the mixed solution is adjusted to 2-4, preferably 2-3, and exemplary 2, 2.5, 3, 4, before the solvent is evaporated; more preferably 2.5.
According to an embodiment of the present invention, sulfuric acid may be added to the mixed solution to adjust the pH of the mixed solution.
According to an embodiment of the present invention, the temperature of the solvent evaporation reaction is 30-70 ℃, preferably 50-70 ℃, and exemplified by 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃; more preferably 60 ℃.
According to an embodiment of the invention, the solvent is evaporated until crystals are obtained. For example, the solvent evaporation reaction time is 48 to 96 hours, preferably 60 to 84 hours, and exemplified by 64 hours.
The total volume of the mixed solution is not particularly limited in the present invention, and for example, the total volume of the mixed solution may be set to 100 to 200mL, and 100mL, 150mL, and 200mL are exemplified according to the growth rule of crystals. By controlling the total volume of the mixed solution within the above range, the evaporation temperature is adjusted so as to promote the solvent to have a sufficiently fast evaporation rate, thereby growing crystals with excellent crystallization and performance. However, if the evaporation rate is too slow, the methyl urea in the solution will undergo hydrolysis reaction with the acid, generating ammonium ions while consuming the acid in the solution, thereby raising the pH of the solution and causing the formation of basic copper sulfate precipitate.
According to an embodiment of the invention, the crystal material Cu of the nickel copper methylurea complex 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The preparation method of the (C) comprises the following steps:
mixing aqueous solution of nickel sulfate hexahydrate, aqueous solution of copper sulfate pentahydrate and aqueous solution of methyl urea, keeping the temperature of each aqueous solution at 30-70 ℃ in the mixing process, then dropwise adding sulfuric acid into the mixed solution, adjusting the pH value of the mixed solution to 2-3, and evaporating, reacting and crystallizing at 30-70 ℃ for 48-96h to obtain the methyl urea nickel copper complex Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 A crystalline material;
wherein, the mol ratio of the nickel sulfate hexahydrate, the copper sulfate pentahydrate and the methyl urea is 0.3:0.7:6.
Specifically, the Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The synthesis process of the crystal material is as follows: 6C (6C) 2 H 6 N 2 O+0.34NiSO 4 ·6H 2 O+0.66CuSO 4 ·5H 2 O→Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 +5.34H 2 O。
The invention also provides the methyl urea nickel-copper complex or the crystal material thereof prepared by the method.
The invention also provides application of the crystal material as a filter material. For example, the filter material is used in a crystal filter device. For example, the crystal filter device is used in an optical device.
The invention also provides a filter material which contains the methyl urea nickel-copper complex crystal material.
The invention also provides a crystal filter device which contains the methyl urea nickel-copper complex crystal material and/or the filter material.
The invention also provides an optical device which contains the methyl urea nickel-copper complex crystal material and/or the filter material and/or the crystal filter device.
The beneficial effects of the invention are that
The invention provides a Cu x Ni 1-x (C 2 H 6 N 2 O) 6 SO 4 (0<x<1) The complex and the crystal material thereof are prepared by spontaneous crystallization after the reaction of nickel sulfate hydrate, copper sulfate hydrate and methyl urea serving as raw materials is completed. The preparation method is simple and convenient to operate.
The crystal material provided by the invention has good transmissivity to blue-green light and strong absorption to near ultraviolet band and near infrared band, and can be used for manufacturingA crystal filter device. For example, cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The crystal material has good transmission performance on green light with the wavelength of 551nm and strong absorption on blue-violet light with the wavelength of 411nm, almost fully absorbs ultraviolet light with the wavelength of 200-370nm and near infrared light with the wavelength of 800-1000nm, can be used for manufacturing crystal filter devices, is applied to optical devices, and has high practicability.
Drawings
FIG. 1 shows the crystalline material Cu prepared in example 1 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 Structure and atomic number diagram of (a).
FIGS. 2 to 5 show the crystalline material Cu prepared in example 1 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 A unit cell stack view viewed in different directions; wherein fig. 2 is a unit cell stack view as viewed in any direction; FIG. 3 is a unit cell stack view as viewed along the a-axis; FIG. 4 is a unit cell stacking view as viewed along the b-axis; fig. 5 is a unit cell stacking diagram as viewed along the c-axis.
FIG. 6 shows the crystalline material Cu prepared in example 1 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 And (c) simulated powder diffraction patterns (c).
FIG. 7 shows the crystalline material Cu prepared in example 1 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 Is a real image of (a).
FIG. 8 shows the crystalline material Cu prepared in example 1 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 Ultraviolet visible transmission spectrum curve of (c).
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Preparing Cu by adopting an aqueous solution evaporation method 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The crystal material comprises the following specific steps:
(1) 0.6mol of methyl urea was dissolved in 50mL of deionized water;
(2) 0.03mol of nickel sulfate hexahydrate was dissolved in 15mL of deionized water;
(3) 0.07mol of copper sulfate pentahydrate was dissolved in 35mL of deionized water;
(4) filtering the methyl urea aqueous solution, the nickel sulfate aqueous solution and the copper sulfate aqueous solution by adopting a filter membrane with the aperture of 1 mu m;
(5) mixing the three aqueous solutions, and heating the mixed solution to 60 ℃;
(6) after the mixed solution is clarified, sulfuric acid is added dropwise, and the pH value of the mixed solution is adjusted to 2.5;
(7) placing the above mixed solution in a culture dish, sealing with fresh-keeping film, needling 15-20 small holes, and evaporating at 60deg.C for 64 hr to obtain Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 Crystalline material.
The reaction equation is as follows: 6C (6C) 2 H 6 N 2 O+0.34NiSO 4 ·6H 2 O+0.66CuSO 4 ·5H 2 O→Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 +5.34H 2 O。
Yellow-green transparent bulk crystals (shown in figure 7) with the sizes of 1mm multiplied by 0.5mm, which are prepared by the method, are selected and placed on an UltraX-Saturn724 small molecule single crystal diffractometer for diffraction experiments. Irradiation with Mo-K.alpha.at 293KData is collected in an omega scan. The result showed that the molecular weight of the crystals was 604.13 and the density was 1.43g/cm 3 F (000) =1902, belonging to the trigonal system, the space group is R-3c, the unit cell parameters areα=90°, β=90°, γ=120°, unit cell volume +.>Number of molecules in unit cell z=6. The crystal structure is shown in fig. 1, and the unit cell stacking diagrams observed in different directions are shown in fig. 2 to 5. In addition, since the ionic radii of nickel and copper metal ions are close in the complex crystal material, the nickel and copper metal ions are difficult to distinguish in single crystal structure analysis, and M in FIGS. 1 to 5 represents Ni and Cu.
The crystals prepared in this example were ground to a finer powder using an agate mortar and ICP was performed using a ulma 2 plasma emission spectrometer to determine the content of nickel and copper metal ions in the molecular formula of the complex crystal material. The test results show that: the complex crystal material prepared in this example had a nickel content of 2.97% and a copper content of 6.23%, i.e., a molar ratio of nickel to copper of 0.34:0.66, and thus the molecular formula of the crystal material prepared in this example was Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 。
The obtained Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The crystals were ground to finer powder with an agate mortar, and after tabletting powder X-ray diffraction data were collected on a Miniflex 600 diffractometer using Cu-ka radiation, scanning range 5-50 °. Comparing the powder diffraction pattern (lower) simulated by the data collected by single crystal diffraction with the diffraction pattern (upper) obtained by actual test, the results are shown in FIG. 6, from which it is known that both are identical in peak position, thereby showing the Cu actually grown in example 1 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The crystal material is successfully prepared and has higher purity.
Cu prepared in this example 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The transmission spectrum of the crystal sample was measured by using a Lambda950 ultraviolet spectrophotometer, and the test result is shown in fig. 8. The results in fig. 8 show that: cu obtained in this example 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The crystal material has a maximum ultraviolet absorption characteristic peak at 551nm and the transmittance thereof is 48.8%, thereby showing that the crystal material has good transmittance to blue light with the wavelength of 551 nm; and from the results in the figures it can be seen that: cu obtained in this example 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The transmittance of the crystal material at 411nm is only 4.2%, so that the crystal material has stronger absorption to blue-violet light with the wavelength of about 411 nm; at the same time, the crystal material almost fully absorbs 200-370nm ultraviolet light and 800-1000nm near infrared light, and the spectral characteristics show that the Cu prepared in the embodiment 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The crystal material can be used for manufacturing a crystal filter device and is applied to an optical device.
Example 2
Preparing Cu by adopting an aqueous solution evaporation method 0.51 Ni 0.49 (C 2 H 6 N 2 O) 6 SO 4 A crystalline material substantially the same as the method of example 1, except that: the molar ratio of nickel sulfate hexahydrate to copper sulfate pentahydrate was 1:1, and the molar amount of both was 0.05mol.
The crystal prepared in this example was pulverized into finer powder with an agate mortar, and ICP test was performed using a ulma 2 plasma emission spectrometer, and the test result showed that the material had a nickel content of 4.61% and a copper content of 4.8%, i.e., the molar ratio of nickel to copper was 0.49:0.51, to thereby obtain a crystal material having a molecular formula of Cu 0.51 Ni 0.49 (C 2 H 6 N 2 O) 6 SO 4 。
Example 3
Preparing Cu by adopting an aqueous solution evaporation method 0.32 Ni 0.68 (C 2 H 6 N 2 O) 6 SO 4 A crystalline material substantially the same as the method of example 1, except that: the molar amount of nickel sulfate hexahydrate was 0.07 mole and the molar amount of copper sulfate pentahydrate was 0.03 mole.
The crystal prepared in this example was pulverized into finer powder with an agate mortar, and ICP test was performed using a ulma 2 plasma emission spectrometer, and the test result showed that the nickel content of the material was 6.49% and the copper content was 2.97%, i.e., the molar ratio of nickel to copper was 0.68:0.32, thereby obtaining a crystal material having a molecular formula of Cu 0.32 Ni 0.68 (C 2 H 6 N 2 O) 6 SO 4 。
Example 4
Preparing Cu by adopting an aqueous solution evaporation method 0.89 Ni 0.11 (C 2 H 6 N 2 O) 6 SO 4 A crystalline material substantially the same as the method of example 1, except that: the molar amount of nickel sulfate hexahydrate was 0.01 mole and the molar amount of copper sulfate pentahydrate was 0.09 mole.
The crystal prepared in this example was pulverized into finer powder with an agate mortar, and ICP test was performed using a Ultima 2 plasma emission spectrometer, and the test result showed that the nickel content in the material was 1.06%, the copper content was 8.80%, i.e., the molar ratio of nickel to copper was 0.11:0.89, thereby obtaining the crystal material having the molecular formula Cu 0.89 Ni 0.11 (C 2 H 6 N 2 O) 6 SO 4 。
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (41)
1. A methylurea nickel-copper complex is characterized in that,the methyl urea nickel copper complex adopts Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 And (3) representing.
2. A crystal material of a methylurea nickel-copper complex is characterized in that the crystal material of the methylurea nickel-copper complex adopts Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 And (3) representing.
3. The crystalline material of methylurea nickel copper complex according to claim 2, wherein the crystalline material belongs to a trigonal system, the space group is R-3c, and the unit cell parameters are a= 10.9701 (5) a, b= 10.9701 (5) a, c= 40.377 (4) a, α=90°, β=90°, γ=120°.
4. The crystalline copper nickel methylurea complex material of claim 2, wherein the crystalline material has a unit cell volume of 4208.1 (5) a 3 。
5. The crystalline copper nickel methylurea complex material according to claim 2, wherein the number of molecules in the unit cell of the crystalline material Z = 6.
6. The crystalline material of methylurea nickel copper complex according to claim 2, wherein the crystalline material has a molecular weight of 604.13 and a density of 1.43g/cm 3 ，F(000)＝1902。
7. The crystalline material of methylurea nickel copper complex according to claim 2, wherein the crystalline material is a yellow-green transparent bulk material.
8. The crystalline material of methylurea nickel copper complex according to claim 7, wherein the crystalline material is a millimeter-sized transparent bulk material; wherein the millimeter scale means that the dimension in at least two dimensions is at least 1mm.
9. The method for preparing the methylurea nickel copper complex according to claim 1 and/or the crystalline material according to any one of claims 2 to 8, wherein the preparation method comprises crystallizing methyl urea, nickel sulfate hydrate, copper sulfate hydrate and a solvent by solvent solution evaporation reaction to obtain the methylurea nickel copper complex and/or the crystalline material.
10. The process according to claim 9, wherein the molar ratio of hydrated sulfate to methyl urea is 1 (5.5-6.5), and the hydrated sulfate is nickel sulfate hydrate and copper sulfate hydrate.
11. The method of claim 9, wherein the molar ratio of nickel sulfate hydrate to copper sulfate hydrate is x (1-x), 0< x <1.
12. The method of claim 11, wherein 0.1.ltoreq.x.ltoreq.0.8.
13. The method of preparation of claim 9, wherein the nickel sulfate hydrate is selected from nickel sulfate hexahydrate and/or nickel sulfate heptahydrate.
14. The method of preparation according to claim 9, wherein the copper sulphate hydrate is selected from copper sulphate pentahydrate and/or copper sulphate monohydrate.
15. The method of claim 9, wherein the solvent is water.
16. The production method according to claim 9, wherein the methyl urea, nickel sulfate hydrate and copper sulfate hydrate are mixed in the form of aqueous solutions thereof or mixed by adding methyl urea, nickel sulfate hydrate and copper sulfate hydrate to water before the solvent solution is evaporated for reaction.
17. The method according to claim 16, wherein the aqueous solution of methyl urea, the aqueous solution of nickel sulfate hydrate and the aqueous solution of copper sulfate hydrate are prepared separately, and the three aqueous solutions are mixed to obtain a mixed solution.
18. The method according to claim 17, wherein the aqueous solution of nickel sulfate hydrate, the aqueous solution of copper sulfate hydrate, and the aqueous solution of methyl urea are mixed during the preparation to completely dissolve the raw materials.
19. The method of claim 18, wherein the three aqueous solutions are further filtered separately prior to mixing the three aqueous solutions.
20. The method of claim 18, wherein the three solutions are mixed and the mixed solution is filtered.
21. The method of claim 19 or 20, wherein the filtration is performed using a microporous filter membrane.
22. The method according to claim 21, wherein the filtration is performed with a filter having a pore size of 0.05 to 1 μm.
23. The method of claim 17, wherein the mixed solution is a clear solution.
24. The method of claim 23, wherein heating is performed during mixing of the three aqueous solutions to obtain a clarified mixed solution; alternatively, the three solutions may be mixed and then heated to obtain a clear mixed solution.
25. The method of claim 24, wherein the heating is at a temperature of 30-70 ℃.
26. The method of claim 25, wherein the heating is at a temperature of 50-70 ℃.
27. The method according to claim 9, wherein the pH of the mixed solution is adjusted to 2-4 before the solvent solution is evaporated.
28. The method of claim 27, wherein the pH of the mixed solution is adjusted to 2-3 prior to the solvent solution being evaporated.
29. The method of claim 27, wherein sulfuric acid is added to the mixed solution to adjust the pH of the mixed solution.
30. The method of claim 9, wherein the solvent solution is evaporated at a temperature of 30-70 ℃.
31. The method of claim 30, wherein the solvent solution is evaporated at a temperature of 50-70 ℃.
32. The method of claim 9, wherein the solvent solution is evaporated until crystals are obtained.
33. The method of claim 32, wherein the solvent solution is evaporated for a period of 48-96 hours.
34. The method of claim 33, wherein the solvent solution is evaporated for a period of time ranging from 60 to 84 hours.
35. The method according to claim 9, wherein the crystal material Cu of the methylurea nickel copper complex 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 The preparation method of the (C) comprises the following steps:
mixing aqueous solution of nickel sulfate hexahydrate, aqueous solution of copper sulfate pentahydrate and aqueous solution of methyl urea, keeping the temperature of each aqueous solution at 30-70 ℃ in the mixing process, then dropwise adding sulfuric acid into the mixed solution, adjusting the pH value of the mixed solution to 2-3, and evaporating, reacting and crystallizing at 30-70 ℃ for 48-96h to obtain the methyl urea nickel copper complex Cu 0.66 Ni 0.34 (C 2 H 6 N 2 O) 6 SO 4 Crystalline material.
36. Use of a methylurea nickel copper complex according to claim 1 and/or a crystalline material according to claim 2 and/or a crystalline material obtained by a method according to any one of claims 9 to 35 as a filter material.
37. The use of claim 36, wherein the filter material is for a crystal filter device.
38. The use of claim 37, wherein the crystal filter device is used in an optical device.
39. A filter material, characterized in that it comprises the methylnickel-copper urea complex according to claim 1 and/or the crystalline material according to claim 2 and/or the crystalline material of the methylnickel-copper urea complex prepared by the preparation method according to any one of claims 9 to 35.
40. A crystal filter device, characterized in that the crystal filter device comprises the methylnickel-copper urea complex according to claim 1 and/or the crystal material according to claim 2 and/or the crystal material of the methylnickel-copper urea complex prepared by the preparation method according to any one of claims 9 to 35 and/or the filter material according to claim 39.
41. An optical device comprising the nickel copper methylurea complex according to claim 1 and/or the crystalline material according to claim 2 and/or the crystalline material of nickel copper methylurea complex according to any one of claims 9 to 35 and/or the filter material according to claim 39 and/or the crystalline filter device according to claim 40.
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| WANG Wen-Ting et al..Synthesis, Structure and Photophysical Properties of a New Complex: Co0.5Ni0.5(C2H6N2O)6SO4.《 Chinese J. Struct. Chem.》.2017,第36卷(第8期),1264-1270. * |
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