CN110002466A - Ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect and preparation method thereof - Google Patents
Ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect and preparation method thereof Download PDFInfo
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- CN110002466A CN110002466A CN201910349016.6A CN201910349016A CN110002466A CN 110002466 A CN110002466 A CN 110002466A CN 201910349016 A CN201910349016 A CN 201910349016A CN 110002466 A CN110002466 A CN 110002466A
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- manganese
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- prussian blue
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910001868 water Inorganic materials 0.000 title claims abstract description 73
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000013078 crystal Substances 0.000 title claims abstract description 64
- 239000013225 prussian blue Substances 0.000 title claims abstract description 60
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 59
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 56
- -1 cyanogen manganese potassium Chemical compound 0.000 title claims abstract description 56
- 230000007547 defect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000008139 complexing agent Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 239000000276 potassium ferrocyanide Substances 0.000 claims abstract description 25
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 17
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011564 manganese citrate Substances 0.000 claims description 3
- 235000014872 manganese citrate Nutrition 0.000 claims description 3
- 229940097206 manganese citrate Drugs 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 78
- 238000001556 precipitation Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000036632 reaction speed Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 12
- 229910052738 indium Inorganic materials 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000001757 thermogravimetry curve Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 241001062009 Indigofera Species 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 238000002524 electron diffraction data Methods 0.000 description 4
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical class [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229960003975 potassium Drugs 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- OTTBJSDTADCRGG-UHFFFAOYSA-N O.[K].[K] Chemical compound O.[K].[K] OTTBJSDTADCRGG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- LSKSRIKESDGPBR-UHFFFAOYSA-N manganese oxalonitrile Chemical compound N#CC#N.[Mn] LSKSRIKESDGPBR-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/14—Cyanic or isocyanic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses ferrous cyanogen manganese potassium prussian blue cubic crystals of a kind of low water low defect and preparation method thereof, belong to field of material synthesis technology.The present invention is in order to solve [the Fe (CN) of ferrous cyanogen manganese potassium prussian blue material6]4‑Defect and the higher technical problem of the crystallization water, provide a kind of ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect, chemical general formula KxMn[Fe(CN)6]1‑y□y·zH2O, 1.9≤x≤2.1,0≤y≤0.03,0≤z≤0.2, crystallization water mass content is less than 1%.The present invention uses soluble manganese salt and potassium ferrocyanide for raw material, by optimization complexing agent and reaction temperature, effectively reduces too fast precipitation reaction speed, extends crystal growth time, to achieve the purpose that reduce defect and the crystallization water in Prussian blue crystalloid.To obtain the prussian blue cubic crystal of the near stoichiometric proportion of high quality.
Description
Technical field
The invention belongs to field of material synthesis technology, and in particular to a kind of ferrous cyanogen manganese potassium of low water low defect is Prussian blue
Class cubic crystal and preparation method thereof.
Background technique
Prussian blue (Prussian Blue, abbreviation PB), i.e. ferric ferrocyanide, chemical formula Fe4[Fe(CN)6]3, most start
It is to be synthesized by German Diesbach in 18 beginnings of the century.As its name suggests, Prussian blue earliest as a kind of vivid
Dyestuff is applied to industrial dyeing, paint ink and other fields relevant to color.If with other transition metal come generation
For the part Fe in Prussian blue, and the alkali or alkaline earth metal element of proper content is introduced, then can be obtained much has class
Like the material of structure, referred to as prussian blue material (Prussian Blue Analogues, abbreviation PBA), general formula AxMy
[Fe(CN)6]1-y□y·zH2O, A represent alkali or alkaline earth metal element, and M represents transition metal element, and represents [M'
(CN)6]4-Defect, z represent the number of the crystallization water contained in single structure cell.In prussian blue material lattice, metal and ferrous iron
Cyanogen root is arranged to form three-dimensional structure skeleton by Fe-C ≡ N-M, and Fe ion and metal M ion are arranged by cubic, and C ≡ N is located at
On the rib of cube, be it is a kind of have open metallo-organic framework structure (metal-organic framework,
MOFs).It has the frame structure and open macrovoid, site of rigidity, forms the structure of similar molecular sieve, synthesis
Process is simple, nontoxic and low in cost, so that this kind of material is suitable for large-scale production.With the continuous depth recognized this kind of material
Enter, application field is also gradually widened.In recent years, Prussian-blue is in electrochemical energy storage, biosensor, low molecule
Magnet, treatment of cancer, the research in the fields such as electrochromic device and application value are outstanding day by day.
Currently, Prussian blue and the like mainly pass through electrochemical deposition method, chemical precipitation method, continuous ionic absorption
It is prepared by method, reverse microemulsion glue method etc..Wherein, chemical precipitation method has many advantages, such as that technique is simple, low in cost, becomes such material
Expect one of the main stream approach being synthetically prepared.Chemical precipitation method, which is based primarily upon, precipitates dissolution equilibrium principle, and prussian blue chemical combination
The solubility product constant of object is smaller by (usually less than 10-13), it means that its precipitation reaction rate is exceedingly fast, so that atomic arrangement is chaotic,
Generate a large amount of [Fe (CN)6]4-Lattice defect.These [Fe (CN)6]4-Defect can reduce alkali metal atom content in lattice, make
It is hung at single transition metal, hydrone can maintain stable structure with transition metal atoms coordination at this time, form coordination crystallization
Water.In addition, the hole of Prussian-blue is in addition to accommodating alkali metal atom, moreover it is possible to store a large number of water molecules, these gaps
Type hydrone and above-mentioned water of coordination molecule constitute the crystallization water of Prussian-blue simultaneously, mass fraction often beyond
10%.In addition, too fast settling velocity can also make material reunite, particle size distribution is uneven.Above defect, crystallization
Water and reunion pattern can all directly affect the performance of Prussian-blue device.
Ferrous cyanogen manganese potassium is a kind of manganese iron series prussian blue material, have it is at low cost, it is resourceful and environmental-friendly
The features such as, show one's talent in numerous Prussian-blues.The chemical formula of ferrous cyanogen manganese potassium can be expressed as KxMn[Fe
(CN)6]1-y□y·zH2O, wherein indicates [Fe (CN)6]4-Defect, H2O is the crystallization water.With other prussian blue material phases
Seemingly, practical to synthesize in resulting ferrous cyanogen manganese potassium all containing a large amount of crystallization water and [Fe due to precipitation reaction excessive velocities
(CN)6]4-Defect.Such as: J.Mater.Chem.A, 2017,5,4325-4330, which disclose a kind of group, becomes K1.75Mn[Fe
(CN)6]0.93□0.07·0.16H2The ferrous cyanogen manganese potassium material of O, [Fe (CN)6]4-Ratio of defects is 7%, the branch provided according to it
Message file is held, the practical crystal water content of the sample is 3.2%, therefore corresponding composition should be K1.75Mn[Fe(CN)6]0.93
□0.07·0.58H2O；Electrochim.Acta, 2012,62,139-145, which disclose a kind of group, becomes K0.1Mn[Fe
(CN)6]0.7□0.3·3.6H2The iron cyanogen manganese potassium material of O, crystal water content 23.8%, [Fe (CN)6]3-Ratio of defects is up to
30%；Chem.Commun., 2017,53,5569 a kind of group is disclosed as K1.67Mn[Fe(CN)6]0.91□0.09·0.73H2O
Ferrous cyanogen manganese potassium material, crystal water content 4.05%, [Fe (CN)6]4-Defect is 9%；J.Am.Chem.Soc.2017,
139,2164-2167, which discloses a kind of group, becomes K1.89Mn[Fe(CN)6]0.92□0.08·0.75H2The ferrous cyanogen manganese potassium material of O,
Its crystal water content is 4%, [Fe (CN)6]4-Defect reaches 8%.
The crystallization water in prussian blue material can be removed using physical method, for example, CN109292795A is disclosed
One kind is heat-treated ferrous cyanogen manganese sodium prussian blue material under atmosphere of inert gases, to reduce sample crystallization water
Method；J.Am.Chem.Soc.2015,137,2658-2664 discloses a kind of ferrous cyanogen manganese sodium of method removal by high vacuum
The method of prussian blue material crystalline water.Although the subsequent processing under inert gas or high vacuum condition can make the crystallization water de-
Out, but these post-processings can consume mass energy, cause unnecessary waste, greatly increase material preparation cost；In addition,
The physical method removal of the crystallization water can not reduce the height [Fe (CN) in original material6]4-Ratio of defects, and put after deviating from the crystallization water
It sets and is easy to absorb moisture content again in air, be restored to original Gao Shuigao defect state.Therefore, how to pass through compounding design,
It is aobvious that one step directly prepares the ferrous cyanogen manganese potassium prussian blue material with high crystalline, low crystal water content and Low Defectivity
It obtains very crucial.
Summary of the invention
The invention solves [the Fe (CN) of ferrous cyanogen manganese potassium prussian blue material in the prior art6]4-Defect and crystallization
The higher technical problem of water content.
The present invention is in order to solve the above technical problems, the ferrous cyanogen manganese potassium for providing firstly a kind of low water low defect is Prussian blue
Class cubic crystal, chemical general formula KxMn[Fe(CN)6]1-y□y·zH2O；Wherein, 1.9≤x≤2.1,0≤y≤0.03,
0≤z≤0.2, crystallization water mass content indicate [Fe (CN) less than 1%,6]4-Defect.
Preferably, the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above, 1.98≤x≤
2.02,0≤y≤0.03,0≤z≤0.15, crystallization water mass content is less than 1%.
Wherein, the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above has high knot
Sharp-featured cube pattern, having a size of 1~5 μm, soilless sticking phenomenon between crystal grain is presented in crystalline substance, single crystal grain.
The present invention also provides the preparation sides of the ferrous cyanogen manganese potassium prussian blue cubic crystal of above-mentioned low water low defect
Method comprising following steps:
A, in deionized water by potassium ferrocyanide and complexing agent dissolution, solution A is obtained；Potassium ferrocyanide in the solution A
Molar ratio with complexing agent is 1:20~100；
B, soluble manganese salt is dissolved in deionized water, obtains solution B；
C, solution B is instilled in solution A, insulation reaction, after reaction, through cooling, separation of solid and liquid, washing and drying,
Obtain ferrous cyanogen manganese potassium prussian blue cubic crystal.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step A, the concentration of potassium ferrocyanide is 0.02~0.2M in the solution A.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step A, the complexing agent is the mixing complexing agent that sylvite complexing agent is 0.2~4 according to molar ratio with sodium salt complexing agent；
Wherein sylvite complexing agent is selected from least one of potassium citrate, potassium oxalate, EDTAP dipotassium ethylene diamine tetraacetate or potassium acetate, sodium salt network
Mixture is selected from least one of sodium citrate, sodium oxalate, disodium ethylene diamine tetraacetate or sodium acetate.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step A, keeping the temperature of solution A is 70~95 DEG C.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step B, the solubility manganese salt is one of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate or manganese citrate or more
Kind.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step B, the concentration of manganese ion is 0.1~2.0M in the solution B.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step B, keeping the temperature of solution B is 70~95 DEG C.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step C, when dropwise addition, the molar ratio for controlling soluble manganese salt and potassium ferrocyanide is 1~3:1.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step C, the rate of addition that solution B instills solution A is 0.1~5mL/min.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step C, the temperature of the insulation reaction is 70~95 DEG C, and the time is 10~36h.
Wherein, the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect described above
In, in step C, the temperature of the drying is 60~120 DEG C, and the time is 2~12h.
Beneficial effects of the present invention:
The present invention uses soluble manganese salt and potassium ferrocyanide for raw material, passes through high temperature, high concentration complexing agent optimum synthesis
Path effectively reduces the initial stage nucleation rate of precipitation reaction, has sufficiently promoted ion and crystal growth, to reach simultaneously
Reduce the purpose of the defects of manganese iron series prussian blue material and the crystallization water；It is verified through being repeated several times, this kind of method can be grown
The Prussian blue analogue crystal close to stoichiometric ratio of high quality out, crystallinity is high, and particle size distribution is uniform, in cube shaped
Looks, no particle agglomeration phenomenon；The potassium content that the method for the present invention has focused on solving synthetic sample is low, the crystallization water and [Fe (CN)6]4-It lacks
The problems such as content is high is fallen into, has the characteristics that green is convenient, easily operated, there is good economy and application value.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of 1 resulting materials of embodiment.
Fig. 2 is 2 μm of scanning electron microscopic picture of 1 resulting materials of embodiment.
Fig. 3 is 50 μm of scanning electron microscopic picture of 1 resulting materials of embodiment.
Fig. 4 is the electron diffraction pattern of 1 resulting materials of embodiment.
Fig. 5 is the thermal gravimetric analysis curve of 1 resulting materials of embodiment.
Fig. 6 is the X ray diffracting spectrum of 2 resulting materials of embodiment.
Fig. 7 is 2 μm of scanning electron microscopic picture of 2 resulting materials of embodiment.
Fig. 8 is 50 μm of scanning electron microscopic picture of 2 resulting materials of embodiment.
Fig. 9 is the electron diffraction pattern of 2 resulting materials of embodiment.
Figure 10 is the thermal gravimetric analysis curve of 2 resulting materials of embodiment.
Figure 11 is the X ray diffracting spectrum of 1 resulting materials of comparative example
Figure 12 is 5 μm of scanning electron microscopic picture of 1 resulting materials of comparative example.
Figure 13 is the thermal gravimetric analysis curve of 1 resulting materials of comparative example.
Figure 14 is the X ray diffracting spectrum of 2 resulting materials of comparative example.
Figure 15 is 5 μm of scanning electron microscopic picture of 2 resulting materials of comparative example.
Figure 16 is the thermal gravimetric analysis curve of 2 resulting materials of comparative example.
Figure 17 is the X ray diffracting spectrum of 3 resulting materials of comparative example.
Figure 18 is 3 μm of scanning electron microscopic picture of 3 resulting materials of comparative example.
Figure 19 is the thermal gravimetric analysis curve of 3 resulting materials of comparative example.
Specific embodiment
Specifically, the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect, chemical general formula KxMn[Fe
(CN)6]1-y□y·zH2O；Wherein, 1.9≤x≤2.1,0≤y≤0.03,0≤z≤0.2, crystallization water mass content less than 1%,
Indicates [Fe (CN)6]4-Defect.
In traditional precipitating synthesis, because reaction speed is too fast, K ion has little time to fill all gap digits, filling rate
Often below 90%, this, which results in extra gap digit, to be filled by hydrone, generate the gap digit crystallization water of more content；
In addition, a large amount of [Fe (CN) can be generated because reaction speed is too fast6]4-Defect causes transition metal to hang, and causes largely to be coordinated
Hydrone.Too low x and y value will increase the gap digit crystallization water and the content for being coordinated the crystallization water respectively, unfavorable to the performance of material.
The present invention can obtain low-down [Fe (CN) by reducing crystal nucleation and growth6]4-Ratio of defects and very high K ion
Filling rate.Because the frame structure gap size of ferrous cyanogen manganese potassium is largerMuch larger than K+DiameterAt a slow speed
The K ion populations that can be filled in single structure cell under conditions of precipitating and abundant Ion transfer are possible to more than 2.
By advanced optimizing to synthesis condition, the ferrous cyanogen closer to stoichiometric ratio, lower water low defect can be obtained
Manganese potassium prussian blue cubic crystal is measured by thermogravimetric analysis and inductively coupled plasma atomic emission (ICP-AES)
It can determine, 1.98≤x≤2.02,0≤y≤0.02,0≤z≤0.15.
Low water low defect provided by the invention can be determined by X-ray diffraction and transmission electron microscope electronic diffraction
Monocline, space group p2 is presented in ferrous cyanogen manganese potassium prussian blue cubic crystal1/ n, crystallinity is superior, single crystal grain
Sharp-featured cube pattern is presented, having a size of 1~5 μm, soilless sticking phenomenon between crystal grain
The present invention also provides the preparation sides of the ferrous cyanogen manganese potassium prussian blue cubic crystal of above-mentioned low water low defect
Method comprising following steps:
A, in deionized water by potassium ferrocyanide and complexing agent dissolution, solution A is obtained；Potassium ferrocyanide in the solution A
Molar ratio with complexing agent is 1:20~100；
B, soluble manganese salt is dissolved in deionized water, obtains solution B；
C, solution B is instilled in solution A, insulation reaction, after reaction, through cooling, separation of solid and liquid, washing and drying,
Obtain ferrous cyanogen manganese potassium prussian blue cubic crystal.
The present invention can be improved the combination of complexing agent and Mn ion using the complexing agent of high concentration, to realize precipitation process
Middle Mn ion slow release from complex compound, slows down precipitation reaction speed；In addition, the present invention adds while using sylvite complexing agent
A part of sodium salt complexing agent is added to help to improve crystallinity the purpose is to realize the buffering of K ion.In fact, addition sodium salt network
Mixture not will lead to the generation of ferrous cyanogen manganese sodium, because ferrous cyanogen manganese potassium is all than ferrous cyanogen manganese from thermodynamics and crystal structure
Sodium is more stable, therefore it is 0.2~4 that the present invention, which controls sylvite complexing agent and sodium salt complexing agent according to molar ratio, guarantees to deposit in solution
In the K+ of sufficient amount, so that making reaction product all is ferrous cyanogen manganese potassium, avoids Na and participate in reaction.
In the present invention, sylvite complexing agent in potassium citrate, potassium oxalate, EDTAP dipotassium ethylene diamine tetraacetate or potassium acetate extremely
Few one kind, sodium salt complexing agent are selected from least one of sodium citrate, sodium oxalate, disodium ethylene diamine tetraacetate or sodium acetate.
Raw material is mainly potassium ferrocyanide and soluble manganese salt in the present invention, and the solubility manganese salt is manganese sulfate, chlorination
One of manganese, manganese nitrate, manganese acetate or manganese citrate are a variety of.It is the complexing agent with high concentration to matching, reduces reaction speed
Rate, while it is more thorough again to carry out reaction, the concentration that the present invention controls potassium ferrocyanide in solution A is 0.02~0.2M, solution B
The concentration of middle manganese ion is 0.1~2.0M, and the molar ratio of soluble manganese salt and potassium ferrocyanide is 1~3:1.
In order to promote the dissolution of complexing agent and the abundant migration of various ions, the present invention is by the temperature of solution A and solution B
70~95 DEG C are remained, reaction remains at high temperature and carries out close under temperature constant state when making to instill.
Since high concentration complexing agent is dissolved in solution A by the present invention, in step C, solution B is instilled in solution A,
Complexing agent concentration is avoided to be diluted, and controlling rate of addition is 0.1~5mL/min, suitably reduction reaction rate.
Reaction temperature control is also 70~95 DEG C on the basis of using the complexing agent of high concentration by the present invention, higher
Reaction temperature, dissolution sedimentation equilibrium can be deviated to dissolution direction, make the reduction of precipitation reaction rate, to realize homogeneous nucleation and crystalline substance
Body is sufficiently grown, and guarantees the crystallinity of product；At such a temperature, the purpose of 10~36h of insulation reaction is ageing, makes reaction more
It adds entirely, crystallinity is more preferable.
In step C of the present invention, the temperature of the drying is 60~120 DEG C, and the time is 2~12h.
Below by embodiment, invention is further described in detail, but does not therefore limit the scope of the present invention
Among the embodiment described range.
Embodiment 1: high temperature+high complexing agent concentration
A, 0.003mol tri- is hydrated potassium ferrocyanide, 0.1mol trisodium citrate dihydrate and 0.1mol monohydrate potassium
Potassium is dissolved in 100mL deionized water, obtains solution A, and keeping the temperature of solution A is 70 DEG C；Wherein, potassium ferrocyanide and citric acid
The molar ratio of salt complexing agent is 1:67；
B, tetra- nitric hydrate manganese of 0.006mol is dissolved in 50mL deionized water, obtains solution B, keep the temperature of solution B
It is 70 DEG C；
C, solution B is instilled in solution A with the speed of 0.5mL/min, 70 DEG C of reaction 12h is kept the temperature, after reaction, through cold
But, sediment is repeatedly washed to centrifuge separation, finally dries 12h in a conventional oven at 80 DEG C, obtains the ferrous general Shandong of cyanogen manganese potassium
Scholar's indigo plant class cubic crystal.
Fig. 1 is the X ray diffracting spectrum of the present embodiment resulting materials, and Fig. 2 and Fig. 3 are the scanning electron microscopic picture of the material,
Fig. 4 is the electron diffraction pattern of the material, it can be seen that it is p2 that the structure of the embodiment resulting materials, which belongs to space group,1/ n's
1~2 μm of cube monocrystalline is presented in ferrous cyanogen manganese potassium structure, single crystal grain, and overall distribution is uniform, favorable dispersibility；Fig. 5 is should
The thermal gravimetric analysis curve of material, measuring crystal water content is 0.6%；Through inductively coupled plasma atomic emission (ICP-AES)
Measurement, the molecular formula of the material are determined as K1.98Mn[Fe(CN)6]0.98□0.02·0.11H2O。
Embodiment 2: high temperature+high complexing agent concentration
A, 0.003mol tri- potassium ferrocyanide, 0.03mol sodium oxalate and 0.03mol potassium oxalate is hydrated to be dissolved in 50mL and go
In ionized water, solution A is obtained, keeping the temperature of solution A is 95 DEG C；The molar ratio of the potassium ferrocyanide and oxalates complexing agent is
1:20；
B, 0.0045mol Manganous sulfate monohydrate is dissolved in 100mL deionized water, obtains solution B, keep the temperature of solution B
Degree is 95 DEG C；
C, solution B is instilled in solution A with the speed of 1mL/min, keeps the temperature 95 DEG C of reaction 2h, after reaction, through cooling,
Sediment is repeatedly washed to centrifuge separation, finally dries 12h in a conventional oven at 80 DEG C, it is Prussian blue to obtain ferrous cyanogen manganese potassium
Class cubic crystal.
Fig. 6 is the X ray diffracting spectrum of the present embodiment resulting materials, and Fig. 7 and Fig. 8 are the scanning electron microscopic picture of the material,
Fig. 9 is the electron diffraction pattern of the material, it can be seen that it is p2 that the structure of the resulting material of the case study on implementation, which belongs to space group,1/
2~3 μm of cube monocrystalline is presented in the ferrous cyanogen manganese potassium structure of n, single crystal grain, and overall distribution is uniform, favorable dispersibility；Figure 10
For the thermal gravimetric analysis curve of the material, measuring crystal water content is 0.5%；Through inductively coupled plasma atomic emission (ICP-
AES it) measures, the molecular formula of the material is determined as K2.02Mn[Fe(CN)6]0.99□0.01·0.10H2O。
Comparative example 1: low temperature+high complexing agent concentration
A, 0.003mol tri- is hydrated potassium ferrocyanide, 0.1mol trisodium citrate dihydrate and 0.1mol monohydrate potassium
Potassium is dissolved in 100mL deionized water, obtains solution A, and keeping the temperature of solution A is 50 DEG C；The potassium ferrocyanide and citric acid
The molar ratio of salt complexing agent is 1:67；
B, tetra- nitric hydrate manganese of 0.006mol is dissolved in 50mL deionized water, obtains solution B, keep the temperature of solution B
It is 50 DEG C；
C, solution B is instilled in solution A with the speed of 0.5mL/min, 50 DEG C of reaction 12h is kept the temperature, after reaction, through cold
But, sediment is repeatedly washed to centrifuge separation, finally dries 12h in a conventional oven at 80 DEG C, obtains the ferrous general Shandong of cyanogen manganese potassium
Scholar's indigo plant class material.
Figure 11 is the X ray diffracting spectrum of this comparative example resulting materials, and Figure 12 is the scanning electron microscopic picture of the material, can be with
Find out, it is p2 that the structure of the resulting material of the comparative example, which still falls within space group,1The ferrous cyanogen manganese potassium structure of/n, but grain shaped
Shape is irregular, and cube monocrystalline, grain shaped of the average grain size in nanoscale, with embodiment 1 and embodiment 2 is not presented
Looks and size difference are huge, in conjunction with X-ray diffraction it can be seen that apparent diffraction maximum is broadened and is overlapped, show the crystal grain ruler of material
Very little and crystallinity is greatly lowered；Figure 13 is the thermal gravimetric analysis curve of the material, and measuring crystal water content is 4.7%, is much larger than
1%；It is measured through inductively coupled plasma atomic emission (ICP-AES), the molecular formula of the material is determined as K1.85Mn[Fe
(CN)6]0.94□0.06·0.89H2O。
Comparative example 2: high temperature+low complexing agent concentration
A, 0.003mol tri- is hydrated potassium ferrocyanide, mono- citrate hydrate of 0.01mol trisodium citrate dihydrate and 0.01mol
Sour potassium is dissolved in 100mL deionized water, obtains solution A, and keeping the temperature of solution A is 95 DEG C；The potassium ferrocyanide and lemon
The molar ratio of hydrochlorate complexing agent is 1:6.7；
B, tetra- nitric hydrate manganese of 0.006mol is dissolved in 50mL deionized water, obtains solution B, keep the temperature of solution B
It is 95 DEG C；
C, solution B is instilled in solution A with the speed of 0.5mL/min, 95 DEG C of reaction 12h is kept the temperature, after reaction, through cold
But, sediment is repeatedly washed to centrifuge separation, finally dries 12h in a conventional oven at 80 DEG C, obtains the ferrous general Shandong of cyanogen manganese potassium
Scholar's indigo plant class material.
Figure 14 is the X ray diffracting spectrum of this comparative example resulting materials, and Figure 15 is the scanning electron microscopic picture of the material, can be with
Find out, it is p2 that the structure of the resulting material of comparison case, which still falls within space group,1The ferrous cyanogen manganese potassium structure of/n, but with comparison
Example 1 is similar, and grain shape is irregular, cube monocrystalline is not presented, average grain size is in nanoscale, with embodiment 1 and in fact
It applies grain morphology in example 2 and size difference is huge, in conjunction with X-ray diffraction it can be seen that apparent diffraction maximum is broadened and is overlapped,
The crystallite dimension and crystallinity for showing material are greatly lowered；Figure 16 is the thermal gravimetric analysis curve of the material, measures the crystallization water and contains
Amount is 4.1%, is much larger than 1%；It is measured through inductively coupled plasma atomic emission (ICP-AES), the molecular formula of the material is true
It is set to K1.86Mn[Fe(CN)6]0.95□0.05·0.78H2O。
Comparative example 3: low temperature+low complexing agent concentration
A, 0.003mol tri- is hydrated potassium ferrocyanide, mono- citrate hydrate of 0.01mol trisodium citrate dihydrate and 0.01mol
Sour potassium is dissolved in 100mL deionized water, obtains solution A, and keeping the temperature of solution A is 50 DEG C；The potassium ferrocyanide and lemon
The molar ratio of hydrochlorate complexing agent is 1:6.7；
B, tetra- nitric hydrate manganese of 0.006mol is dissolved in 50mL deionized water, obtains solution B, keep the temperature of solution B
It is 50 DEG C；
C, solution B is instilled in solution A with the speed of 0.5mL/min, 50 DEG C of reaction 12h is kept the temperature, after reaction, through cold
But, sediment is repeatedly washed to centrifuge separation, finally dries 12h in a conventional oven at 80 DEG C, obtains the ferrous general Shandong of cyanogen manganese potassium
Scholar's indigo plant class material.
Figure 17 is the X ray diffracting spectrum of this comparative example resulting materials, and Figure 18 is the scanning electron microscopic picture of the material, can be with
Find out, it is p2 that the structure of the resulting material of the comparative example, which still falls within space group,1The ferrous cyanogen manganese potassium structure of/n, but and comparative example
1 is similar with comparative example 2, and grain shape is irregular, and cube monocrystalline is not presented, and average grain size has bright in nanoscale
Grain morphology and size difference in aobvious agglomeration, with embodiment 1 and embodiment 2 is huge, can see in conjunction with X-ray diffraction
Apparent diffraction maximum is broadened and is overlapped out, shows that the crystallite dimension of material and crystallinity are greatly lowered；Figure 19 is the material
Thermal gravimetric analysis curve, measuring crystal water content is 7.5%, is much larger than 1%；Through inductively coupled plasma atomic emission (ICP-
AES it) measures, the molecular formula of the material is determined as K1.52Mn[Fe(CN)6]0.87□0.13·1.35H2O。
By above-described embodiment and comparative example it is found that the present invention passes through high temperature, high concentration complexing agent optimum synthesis path, control
Dropwise addition sequence and speed, effectively reduce the initial stage nucleation rate of precipitation reaction, have sufficiently promoted ion and crystal growth, thus
The defects of achieve the purpose that while having reduced manganese iron series prussian blue material and the crystallization water, can be prepared close to chemistry meter
The Prussian blue analogue crystal of ratio is measured, crystallinity is high, and particle size distribution is uniform, is in cube pattern.
Claims (10)
1. the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect, it is characterised in that: its chemical general formula is KxMn
[Fe(CN)6]1-y□y·zH2O；Wherein, 1.9≤x≤2.1,0≤y≤0.03,0≤z≤0.2, crystallization water mass content are less than
1%, indicate [Fe (CN)6]4-Defect.
2. the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect according to claim 1, feature exist
In: 1.98≤x≤2.02,0≤y≤0.02,0≤z≤0.15.
3. the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect according to claim 1 or 2, feature
Be: sharp-featured cube pattern, having a size of 1~5 μm, nothing between crystal grain is presented with high crystalline, single crystal grain in it
Agglomeration.
4. the preparation method of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect, it is characterised in that: including with
Lower step:
A, in deionized water by potassium ferrocyanide and complexing agent dissolution, solution A is obtained；Potassium ferrocyanide and network in the solution A
The molar ratio of mixture is 1:20~100；
B, soluble manganese salt is dissolved in deionized water, obtains solution B；
C, solution B is instilled in solution A, insulation reaction through cooling, separation of solid and liquid, washing and drying, obtains sub- after reaction
Iron cyanogen manganese potassium prussian blue cubic crystal.
5. the preparation side of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect according to claim 4
Method, it is characterised in that: in step A, at least meet following one:
The concentration of potassium ferrocyanide is 0.02~0.2M in the solution A；
The mixing complexing agent that the complexing agent is sylvite complexing agent and sodium salt complexing agent is 0.2~4 according to molar ratio；Wherein sylvite
Complexing agent is selected from least one of potassium citrate, potassium oxalate, EDTAP dipotassium ethylene diamine tetraacetate or potassium acetate, and sodium salt complexing agent is selected from
At least one of sodium citrate, sodium oxalate, disodium ethylene diamine tetraacetate or sodium acetate；
The temperature for keeping solution A is 70~95 DEG C.
6. the preparation side of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect according to claim 4
Method, it is characterised in that: in step B, at least meet following one:
The solubility manganese salt is one of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate or manganese citrate or a variety of；
The concentration of manganese ion is 0.1~2.0M in the solution B；
The temperature for keeping solution B is 70~95 DEG C.
7. the preparation side of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect according to claim 4
Method, it is characterised in that: in step C, when dropwise addition, the molar ratio for controlling soluble manganese salt and potassium ferrocyanide is 1~3:1.
8. the preparation side of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect according to claim 4
Method, it is characterised in that: in step C, the rate of addition that solution B instills solution A is 0.1~5mL/min.
9. the preparation side of the ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect according to claim 4
Method, it is characterised in that: in step C, the temperature of the insulation reaction is 70~95 DEG C, and the time is 10~36h.
10. according to the ferrous cyanogen manganese potassium prussian blue cubic crystal of the described in any item low water low defects of claim 4~9
Preparation method, it is characterised in that: in step C, the temperature of the drying is 60~120 DEG C, and the time is 2~12h.
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