CN108276992A - 用于白光发射的钙基质稀土有机框架材料及制备方法 - Google Patents
用于白光发射的钙基质稀土有机框架材料及制备方法 Download PDFInfo
- Publication number
- CN108276992A CN108276992A CN201810149041.5A CN201810149041A CN108276992A CN 108276992 A CN108276992 A CN 108276992A CN 201810149041 A CN201810149041 A CN 201810149041A CN 108276992 A CN108276992 A CN 108276992A
- Authority
- CN
- China
- Prior art keywords
- calcium
- white light
- light emission
- rare earth
- framework materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000011575 calcium Substances 0.000 title claims abstract description 53
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 52
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011159 matrix material Substances 0.000 title claims abstract description 49
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 43
- 239000013384 organic framework Substances 0.000 title claims abstract description 34
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 22
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 17
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 159000000007 calcium salts Chemical class 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 150000001217 Terbium Chemical class 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 7
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical class [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 7
- 150000000918 Europium Chemical class 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical class [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 3
- 238000004140 cleaning Methods 0.000 claims 1
- 239000013110 organic ligand Substances 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- -1 rare earth ions Chemical class 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
本发明公开了用于白光发射的钙基质稀土有机框架材料及制备方法,解决了现有技术中并没有公开采用钙为基质制备出白光发射框架材料的报道的问题。本发明中用于白光发射的钙基质稀土有机框架材料,以2,6‑吡啶二羧酸为有机配体,钙为基质,铕、铽共掺构成。本发明还公开了上述用于白光发射的钙基质稀土有机框架材料的制备方法。本发明方法开创性的利用钙为基质,制备出白光发射的框架材料,为白光发射稀土有机框架材料的制备提供多一种生产途径,该材料发光强度增强并且稳定性更好,本发明方法相比现有材料多步骤的合成工艺更简化高效,设备更简单,成本大大降低。
Description
技术领域
本发明属于发光材料技术领域,具体涉及用于白光发射的钙基质稀土有机框架材料及制备方法。
背景技术
白光LED由于其发光效率高、寿命长、器件小、响应快等特点,近十几年以来发展迅速,被认为是能取代白炽灯和荧光灯的固态光源。白光LED有多种实现方式,目前最主流的实现方式是蓝光LED芯片激发黄色荧光粉共同形成白光,这种方案具有设计简单、流明效率高等优点。利用多金属有机框架材料可以制备实现单一的荧光粉,在紫外光激发下照射呈显色指数高、色温值符合要求、发光效率提升的白光,因而其材料的设计和制备是具有重要意义的。
金属-有机框架材料(Metal-organic frameworks,简称MOFs)作为一种新型有机无机杂化材料,它是一种以金属离子或金属簇为节点,有机配体作为连接单元,利用金属离子与有机配体之问的配位作用,自组装构建成的周期性一维、二维或三维网络结构的晶体材料。MOFs具有发光机制丰富多样、发光波长范围覆盖广、组分可选择广(特别是有机配体组分)以及结构可调控等多重优势,因此在发光领域有良好的应用前景。MOFs发光材料实现白光发射,目前常采用的方式主要有两种:(1)利用有机配体π-π*的宽谱发射,通过改变激发波长,有效地利用有机配体的跃迁以及MLCT等作用而诱导白光发射,(2)多稀土离子混合的方法,主要是基于二基色或者三基色原理,组合有机配体的蓝光发射以及稀土离子的红光、绿色发射来实现白光发射。
现有技术中相较于第一种方式,后者具有可设计、颜色可调控性强的优势,但是在现有技术中采用第二种方式时,公开的也仅仅只有钆或锌作为基质制备白光发射的稀土有机框架材料的报道,并没有公开采用钙为基质制备出白光发射的稀土有机框架材料的报道。
不同基质的稀土有机框架材料具有丰富的发光位点,其结构中的稀土金属离子、有机配体都可以作为发光单元,与此同时基质离子、多稀土离子、有机配体相互间存在着丰富的能量转移进而诱导不同的发光,因此要得到白光发射的钙基质稀土有机框架材料并不容易,需要钙基质、稀土金属离子、有机配体为一体,密切配合才能发出白光。
发明内容
本发明所要解决的技术问题是:现有技术中没有公开以钙为基质制备出白光发射的稀土有机框架材料的相关报道,本发明提供了一种以钙为基质制备出白光发射的稀土有机框架材料的方法,即用于白光发射的钙基质稀土有机框架材料及其制备方法,该方法能有效利用钙为基质,制备出白光发射的稀土有机框架材料,为白光发射的稀土有机框架材料的制备提供多一种生产途径。
本发明通过下述技术方案实现:
用于白光发射的钙基质稀土有机框架材料,以2,6-吡啶二羧酸为有机配体,钙为基质,铕、铽共掺构成。
进一步,所述2,6-吡啶二羧酸:钙:铕:铽的摩尔比为1.8:0.51~0.52:0.07~0.08:0.01~0.02。
由于每种物质发射的光线色彩是不相同的,原料相同制备工艺不同时,获得产物的维度也可能会相差很大,导致并不是简单的通过色彩的组合就可挑选出适用于钙基质的有机配体和稀土元素,在有机配体和稀土元素无法简单确定的前提下,钙基质与有机配体和稀土元素之间的配比也并不是本行业技术人员能够简单获得的。本发明开创性之处在于以2,6-吡啶二羧酸为有机配体的白光发射MOFs材料中使用钙作为基质,通过铕、铽共掺来制备白光发射的材料,该以钙为基质实现白光发射的目的的有机配体和稀土金属元素及其配比是发明人创造性劳动获得的,制备出的材料能有效达到实现白光发射的目的,效果十分显著。
本发明还提供了用于白光发射的钙基质稀土有机框架材料的制备方法,包括:
a.将2,6-吡啶二羧酸、钙盐、铕盐以及铽盐溶解于混合溶剂中,混匀后在90~100℃恒温密闭反应3~4天,得到粗产物;
b.将粗产物纯化即得用于白光发射的钙基质稀土有机框架材料;
其中,所述2,6-吡啶二羧酸、钙盐、铕盐、铽盐中2,6-吡啶二羧酸:钙:铕:铽的摩尔比为1.8:0.51~0.52:0.07~0.08:0.01~0.02;所述混合溶剂为有机溶剂与水按照体积比为1~2:1的混合溶液,所述有机溶剂为乙醇。
通过本发明上述方法的优化,其不仅仅能有效制备出适用于以钙为基质,铕、铽共掺获得实现白光发射的框架材料,并且该方法更加简单,本发明制备得到的材料为多种金属离子与有机框配体组成的三维胶囊状结构,极大的降低了非辐射跃迁的几率,使得双稀土离子共同发光强度增强,并且稳定性更好。其中,恒温密闭反应防止乙醇与蒸馏水的蒸发同时也避免了外界的影响。
优选地,所述有机溶剂优选为无毒、绿色环保的乙醇。
进一步,所述钙盐为氯化钙、乙酸钙或六水硝酸钙中的至少一种;所述铕盐为六水硝酸铕;所述铽盐为六水硝酸铽。
硝酸钙能够起到转晶剂的作用,有利于得到稳定的结构,同时也有利于钙的取代,因此本次发明的钙盐优选为六水硝酸钙。
进一步,所述2,6-吡啶二羧酸与混合溶剂的摩尔体积比为0.072~0.12mol/L。
进一步,所述纯化的方法包括:将反应得到的粗产物依次进行离心、多次清洗、烘干即可;
其中,所述多次清洗采用有机溶剂与水体积比为1~2:1的混合物,所述有机溶剂为乙醇,
所述多次清洗为3~5次清洗。
本发明具有如下的优点和有益效果:
1、本发明开创性的使用钙作为基质,通过铕、铽共掺和2,6-吡啶二羧作用实现白光发射的目的;
2、本发明的材料为多种金属离子与有机配体组成的三维胶囊状结构,极大的降低了非辐射跃迁的几率,使得双稀土离子共同发光强度增强,并且稳定性更好;
3、本发明有着可设计性的优点,有效提高了双稀土的发光效率,增加了能量的利用效率。并可以通过改变双稀土共掺比例来实现显色指数,发光效率的调节与优化;
4、本发明成功的采用一步合成的方法制备框架材料,相对现有材料多步骤合成工艺而言,制备工艺更简化高效,设备更简单,合成成本大大降低。
附图说明
此处所说明的附图用来提供对本发明实施例的进一步理解,构成本申请的一部分,并不构成对本发明实施例的限定。在附图中:
图1为本发明的Eu3+ 0.12Tb3+ 0.02@CaPDA的发射光谱。
图2为本发明的Eu3+ 0.12Tb3+ 0.02@CaPDA的色度坐标图。
图3为本发明的Eu3+ 0.12Tb3+ 0.02@CaPDA的XRD谱图。
图4为本发明的Eu3+ 0.08Tb3+ 0.2@CadPDA的IR图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,下面结合实施例,对本发明作进一步的详细说明,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为对本发明的限定。
实施例1
用于白光发射的钙基质稀土有机框架材料的制备方法,包括:
将1.8mmol的2,6-吡啶二羧酸配体、0.516mmol的六水硝酸钙、0.072mmol的六水硝酸铕以及0.012mmol的六水硝酸铽溶解于10mL乙醇和10mL水的混合溶剂中,用玻璃棒搅拌均匀后放入密闭的反应釜中,在90~100℃恒温反应3天。反应后对样品进行离心处理,并用无水乙醇与水体积比为1:1的混合溶剂清洗3次样品,烘干后得到以钙为基质的双稀土-有机框架材料,其发射光谱图、色度坐标图、XRD谱图、IR图分别见图1、2、3、4所示。
当激发波长为315nm时,有机配体、铽、铕发射光谱的最强峰分别位于411nm、550nm和617nm,荧光粉的发光为白色,其色坐标为(0.3110,0.3242),在500v电压,狭缝、狭宽均为5nm下测试,发光强度为5000cd。
实施例2
用于白光发射的钙基质稀土有机框架材料的制备方法,包括:
将1.8mmol的2,6-吡啶二羧酸配体、0.514mmol的钙盐六水硝酸钙、0.074mmol的铕盐六水硝酸铕以及0.02mmol的铽盐六水硝酸铽溶解于10mL乙醇和10mL水的混合溶剂中,用玻璃棒搅拌均匀后放入密闭的反应釜中,在90~100℃恒温反应3天。反应后对样品进行离心处理,并用无水乙醇与水体积比为1:1的混合溶剂清洗3次样品,烘干后得到以钙为基质的双稀土-有机框架材料。
当激发波长为315nm时,有机配体、铽、铕发射光谱的最强峰分别位于411nm、546nm和618nm,荧光粉的发光为白色,其色坐标为(0.3000,0.3258)。
实施例3
用于白光发射的钙基质稀土有机框架材料的制备方法,包括:
将1.8mmol的2,6-吡啶二羧酸配体、0.512mmol的钙盐六水硝酸钙、0.076mmol的铕盐六水硝酸铕以及0.02mmol的铽盐六水硝酸铽溶解于10mL乙醇和10mL水的混合溶剂中,用玻璃棒搅拌均匀后放入密闭的反应釜中,在90~100℃恒温反应3天。反应后对样品进行离心处理,并用无水乙醇与水体积比为1:1的混合溶剂清洗3次样品,烘干后得到以钙为基质的双稀土有机框架材料。
当激发波长为315nm时,有机配体、铽、铕发射光谱的最强峰分别位于411nm、546nm和618nm,荧光粉的发光为白色,其色坐标为(0.2996,0.3269)。
实施例4
用于白光发射的钙基质稀土有机框架材料的制备方法,包括:
将1.8mmol的2,6-吡啶二羧酸配体、0.510mmol的钙盐六水硝酸钙、0.078mmol的铕盐六水硝酸铕以及0.02mmol的铽盐六水硝酸铽溶解于10mL乙醇和10mL水的混合溶剂中,用玻璃棒搅拌均匀后放入密闭的反应釜中,在90~100℃恒温反应3天。反应后对样品进行离心处理,并用无水乙醇与水体积比为1:1的混合溶剂清洗3次样品,烘干后得到以钙为基质的双稀土-有机框架材料。
当激发波长为315nm时,有机配体、铽、铕发射光谱的最强峰分别位于411nm、546nm和618nm,荧光粉的发光为白色,其色坐标为(0.2987,0.3301)。
实施例5
用于白光发射的钙基质稀土有机框架材料的制备方法,包括:
将1.8mmol的2,6-吡啶二羧酸配体、0.520mmol的钙盐六水硝酸钙、0.070mmol的铕盐六水硝酸铕以及0.010mmol的铽盐六水硝酸铽溶解于10mL乙醇和10mL水的混合溶剂中,用玻璃棒搅拌均匀后放入密闭的反应釜中,在90~100℃恒温反应3天。反应后对样品进行离心处理,并用乙醇与水体积比为1:1的混合溶剂清洗3次样品,烘干后得到以钙为基质的双稀土-有机框架材料。
当激发波长为315nm时,有机配体、铽、铕发射光谱的最强峰分别位于411nm、546nm和618nm,荧光粉的发光为白色,其色坐标为(0.3001,0.3006)。
由实施例1~5及图1和2可以看出,本发明的荧光粉激发波长为315nm时,有机配体、铽、铕发射光谱的最强峰均分别位于411nm、546nm和618nm,发光为白色,色坐标(0.2986~0.3034,0.3001~0.3269),范围窄,非常接近国际纯白光CIE色度坐标(0.333,0.333)。
由图3可以看出Eu、Tb分布很均匀,纯度接近纯相。
由图4Ca0.86Eu0.12Tb0.02(PDA)3·(H2O)5红外光谱分析图可以看出:在3438cm-1处出现了H-O的伸缩振动峰,1608cm-1处出现了H-O-H的变形振动吸收峰,在1000-1300cm-1处附近出现的C-O键的伸缩振动峰在420-763cm-1处出现了含苯环的C-H振动吸收峰。
以上显示和描述了本发明的基本原理和主要特征及本发明的优点。本行业的技术人员应该了解,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (9)
1.用于白光发射的钙基质稀土有机框架材料,其特征在于:以2,6-吡啶二羧酸为有机配体,钙为基质,铕、铽共掺构成。
2.根据权利要求1所述的用于白光发射的钙基质稀土有机框架材料,其特征在于,所述2,6-吡啶二羧酸:钙:铕:铽的摩尔比为1.8:0.51~0.52:0.07~0.08:0.01~0.02。
3.用于白光发射的钙基质稀土有机框架材料的制备方法,其特征在于,包括:
a.将2,6-吡啶二羧酸、钙盐、铕盐以及铽盐溶解于混合溶剂中,混匀后在90~100℃恒温密闭反应3~4天,得到粗产物;
b.将粗产物纯化即得用于白光发射的钙基质稀土有机框架材料;
其中,所述2,6-吡啶二羧酸、钙盐、铕盐、铽盐中2,6-吡啶二羧酸:钙:铕:铽的摩尔比为1.8:0.51~0.52:0.07~0.08:0.01~0.02;所述混合溶剂为有机溶剂与水按照体积比为1~2:1的混合溶液。
4.根据权利要求3所述的用于白光发射的钙基质稀土有机框架材料的制备方法,其特征在于,所述有机溶剂为乙醇。
5.根据权利要求3所述的用于白光发射的钙基质稀土有机框架材料的制备方法,其特征在于,所述钙盐为氯化钙、乙酸钙或六水硝酸钙中的至少一种;所述铕盐为六水硝酸铕;所述铽盐为六水硝酸铽。
6.根据权利要求5所述的用于白光发射的钙基质稀土有机框架材料的制备方法,其特征在于,所述钙盐优选为六水硝酸钙。
7.根据权利要求3所述的用于白光发射的钙基质稀土有机框架材料的制备方法,其特征在于,所述2,6-吡啶二羧酸与混合溶剂的摩尔体积比为0.072~0.12mol/L。
8.根据权利要求3所述的用于白光发射的钙基质稀土有机框架材料的制备方法,其特征在于,所述纯化的方法包括:将反应得到的粗产物依次进行离心、多次清洗、烘干即可;
其中,所述多次清洗采用有机溶剂与水体积比为1~2:1的混合物(清洗时的混合溶液与制备中的混合溶液相同,并且有机溶剂和水的配比一样,有机溶剂均为乙醇)。
9.根据权利要求8所述的用于白光发射的钙基质稀土有机框架材料的制备方法,其特征在于,所述有机溶剂为乙醇;所述多次清洗为3~5次清洗。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810149041.5A CN108276992A (zh) | 2018-02-13 | 2018-02-13 | 用于白光发射的钙基质稀土有机框架材料及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810149041.5A CN108276992A (zh) | 2018-02-13 | 2018-02-13 | 用于白光发射的钙基质稀土有机框架材料及制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108276992A true CN108276992A (zh) | 2018-07-13 |
Family
ID=62808465
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810149041.5A Pending CN108276992A (zh) | 2018-02-13 | 2018-02-13 | 用于白光发射的钙基质稀土有机框架材料及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108276992A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111909084A (zh) * | 2020-08-24 | 2020-11-10 | 北京石油化工学院 | 一种用于检测DPA的Eu/Tb(BPDC)(NO3)的制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20120082634A (ko) * | 2011-01-14 | 2012-07-24 | 중앙대학교 산학협력단 | 신규한 1차원 나선 사슬 구조의 칼슘-유기골격구조 화합물 |
CN105542751A (zh) * | 2015-12-11 | 2016-05-04 | 广东工业大学 | 一种发射白光的金属有机框架材料及其合成方法和应用 |
US20160152638A1 (en) * | 2014-12-02 | 2016-06-02 | Massachusetts Institute Of Technology | Multistimuli-responsive white luminescent materials including metal elements |
EP3053988A2 (en) * | 2015-02-09 | 2016-08-10 | Information Technology Inc. | Method for fabricating phosphor having maximum absorption wavelength between 410 nm and 470 nm and having no rare earth element therein and method for generating a white light by using the phosphor |
US9741945B1 (en) * | 2013-07-03 | 2017-08-22 | National Technology & Engineering Solutions Of Sandia, Llc | Tunable photoluminescent metal-organic-frameworks and method of making the same |
-
2018
- 2018-02-13 CN CN201810149041.5A patent/CN108276992A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20120082634A (ko) * | 2011-01-14 | 2012-07-24 | 중앙대학교 산학협력단 | 신규한 1차원 나선 사슬 구조의 칼슘-유기골격구조 화합물 |
US9741945B1 (en) * | 2013-07-03 | 2017-08-22 | National Technology & Engineering Solutions Of Sandia, Llc | Tunable photoluminescent metal-organic-frameworks and method of making the same |
US20160152638A1 (en) * | 2014-12-02 | 2016-06-02 | Massachusetts Institute Of Technology | Multistimuli-responsive white luminescent materials including metal elements |
EP3053988A2 (en) * | 2015-02-09 | 2016-08-10 | Information Technology Inc. | Method for fabricating phosphor having maximum absorption wavelength between 410 nm and 470 nm and having no rare earth element therein and method for generating a white light by using the phosphor |
CN105542751A (zh) * | 2015-12-11 | 2016-05-04 | 广东工业大学 | 一种发射白光的金属有机框架材料及其合成方法和应用 |
Non-Patent Citations (4)
Title |
---|
HONGMING HE,等: "Tunable colors and white-light emission based on a microporous luminescent Zn(ii)-MOF", 《DALTON TRANS.》 * |
叶铁林,等: "《化工结晶过程原理及应用》", 30 April 2006, 北京工业大学出版社 * |
周敬修: "基于2,6-吡啶二羧酸的稀土—有机框架材料的制备与白光拟合研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
陈绪港: "基于2,6-吡啶二羧酸的稀土金属—有机框架的合成及发光性能调控研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111909084A (zh) * | 2020-08-24 | 2020-11-10 | 北京石油化工学院 | 一种用于检测DPA的Eu/Tb(BPDC)(NO3)的制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107698775B (zh) | 用于白光发射的多稀土-有机框架材料及其制备方法 | |
CN108690201B (zh) | 一种mof/染料复合的高量子产率白光荧光粉材料及其制备方法 | |
CN109810139B (zh) | 复合季鏻盐及其制备方法与荧光应用 | |
CN108912337B (zh) | 一种高量子产率的稀土金属有机框架材料及其制备方法 | |
CN107226914B (zh) | 一种铽有机骨架配合物及其制备方法 | |
CN112408464B (zh) | 可逆转化铯铜卤素钙钛矿纳米晶体及其制备方法 | |
CN106083841B (zh) | 一种基于二溴1,4‑二丙基‑1,4‑二氮杂二环[2.2.2]辛烷的二价锰荧光材料及其制备方法和应用 | |
CN113355092B (zh) | 一种单基质双发射荧光粉及其制备方法与应用 | |
CN113429963B (zh) | 一种连续变色荧光防伪材料及其制备方法和应用 | |
Li et al. | F enhanced luminescence performance of SrLu2O4: Ce3+ glass ceramic for superior high-power artificial horticultural LEDs | |
CN108192111B (zh) | 一种吡啶酸类金属有机框架白光材料及其制备方法 | |
CN106433617B (zh) | 一种用于调节白光led的荧光化合物及其制备方法和应用 | |
CN106085412B (zh) | 一种基于二溴1,4-二丁基-1,4-二氮杂二环[2.2.2]辛烷的二价锰荧光材料的制备、表征和应用 | |
CN113201328B (zh) | 一种单基质双带白光发射材料及其制备方法与应用 | |
CN114507522A (zh) | 稀土掺杂钙钛矿红光发光材料及其制备方法和应用 | |
CN105018073B (zh) | 一种含有两种配体的Eu配合物红色发光晶体材料及其制备方法 | |
CN107722291B (zh) | 引入有机染料的稀土-有机框架材料及其制备方法 | |
CN108276992A (zh) | 用于白光发射的钙基质稀土有机框架材料及制备方法 | |
CN107163941A (zh) | 一种碱土金属钨钼酸盐红色荧光粉及其制备方法 | |
CN107286350B (zh) | 具有高热稳定性的稀土配位聚合物及其制备方法 | |
CN108164716A (zh) | 制备用于白光发射的钆基质稀土有机MOFs材料的方法 | |
Ding et al. | Single-phase white light material and antibiotic detection of lanthanide metal–organic frameworks | |
CN106318381B (zh) | 一种Mn4+掺杂的氟化氢钠红光材料及其制备方法 | |
CN114605659A (zh) | 一种双螺旋结构的Cd-MOF材料及其制备方法和应用 | |
CN110655915A (zh) | 一种有机无机杂化的稀土复合荧光材料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180713 |
|
RJ01 | Rejection of invention patent application after publication |