Y/Gd/Eu三元稀土层状化合物的离子交换行为与光学性能
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摘要
采用低温液相沉淀技术合成出硝酸盐类Y/Gd/Eu三元体系的稀土层状化合物,通过自组装获得了花瓣状超薄纳米片,并研究了该化合物的硫酸根离子交换行为和光学性能。研究表明,当硫酸根与硝酸根的摩尔比R=0.25时,硫酸根离子可以完全置换层状化合物层间的硝酸根离子。离子交换后层状化合物的发光强度减弱,Gd~(3+)离子掺杂使Eu~(3+)离子的配位环境发生改变,从而导致磁偶极子跃迁~5D_0→~7F_1的2个发射峰的相对强度发生变化。硫酸根离子交换改变了层状化合物的热分解路径,阻碍了煅烧过程中颗粒间的表面扩散,从而获得了高分散的氧化物荧光粉(平均粒度～120nm),该粉体呈现出Eu~(3+)离子的~5D_0→~7F_J的特征红光。Gd~(3+)离子掺杂有效敏化了氧化物固溶体中Eu~(3+)离子的发光,煅烧温度的提高也进一步增加了粉体的发光强度与量子效率,同时缩短了荧光寿命。
Self-assembly layered rare-earth hydroxide(LRH) nanosheets of ternary Y/Gd/Eu system were synthesized by a chemical precipitation route at freezing temperature. The anion-exchange behavior and optical properties of the LRHs were studied. The results show that at the SO_4~(2-)/Ln~(3+) molar ratio(R) of 0.25, the SO_4~(2-) almost replaces the NO_3~- located in the interlayer of the LRH via anion exchange; however, the photoluminescence(PL) intensity decreases. Gd~(3+) substitution for Y~(3+) significantly changes the coordination environment of Eu~(3+), leading to different intensities for the splitting bands of ~5D_0→~7F_J transition peaking at ～590 and 595 nm. Sulfate exchange inhibits surface diffusion and inter-particle sintering during calcination, and thus well-dispersed oxide powders that exhibit typical Eu~(3+) red emission are obtained. The Gd~(3+) addition sensitizes Eu~(3+) emission to enhance the PL intensity of the phosphors. Improved PL intensity and external quantum efficiency and decreased fluorescence lifetime are observed at higher calcination temperatures.
Self-assembly layered rare-earth hydroxide(LRH) nanosheets of ternary Y/Gd/Eu system were synthesized by a chemical precipitation route at freezing temperature. The anion-exchange behavior and optical properties of the LRHs were studied. The results show that at the SO_4~(2-)/Ln~(3+) molar ratio(R) of 0.25, the SO_4~(2-) almost replaces the NO_3~- located in the interlayer of the LRH via anion exchange; however, the photoluminescence(PL) intensity decreases. Gd~(3+) substitution for Y~(3+) significantly changes the coordination environment of Eu~(3+), leading to different intensities for the splitting bands of ~5D_0→~7F_J transition peaking at ～590 and 595 nm. Sulfate exchange inhibits surface diffusion and inter-particle sintering during calcination, and thus well-dispersed oxide powders that exhibit typical Eu~(3+) red emission are obtained. The Gd~(3+) addition sensitizes Eu~(3+) emission to enhance the PL intensity of the phosphors. Improved PL intensity and external quantum efficiency and decreased fluorescence lifetime are observed at higher calcination temperatures.
引文
[1]Hou Wenyan(侯文艳),Liu Zonghuai(刘宗怀),Zhang Guochun(张国春).Materials Review(材料导报)[J],2007,21(1):110
[2]Gándara F,Perles J,Snejko N et al.Angewandte Chemie International Edition[J],2006,45(47):7998
[3]Geng F X,Matsushita Y,Ma R Z et al.Journal of the American Chemical Society[J],2008,130(48):16 344
[4]McIntyre L J,Jackson L K,Fogg A M.Chemistry of Materials[J],2008,20(1):335
[5]Lee K H,Byeon S H.European Journal of Inorganic Chemistry[J],2009(7):929
[6]Lee K H,Byeon S H.European Journal of Inorganic Chemistry[J],2009(31):4727
[7]Geng F X,Ma R Z,Sasaki T.Accounts of Chemical Research[J],2010,43(9):1177
[8]Zhao Y S,Li J G,Guo M X et al.Journal of Materials Chemistry C[J],2013,1(22):3584
[9]Lu B,Li J G,Suzuki T S et al.Journal of the American Ceramic Society[J],2015,98(5):1413
[10]Lu B,Li J G,Suzuki T S et al.Journal of the American Ceramic Society[J],2015,98(8):2480
[11]Lu B,Li J G,Sun X D et al.Journal of the American Ceramic Society[J],2015,98(12):3877
[12]Wakefield G,Holland E,Dobson P J et al.Advanced Materials[J],2001,13(20):1557
[13]Byeon S H,Ko M G,Park J C et al.Chemistry of Materials[J],2002,14(2):603
[14]Hirai T,Hirano T,Komasawa I.Journal of Materials Chemistry[J],2000,10(10):2306
[15]Li J G,Li X D,Sun X D et al.The Journal of Physical Chemistry C[J],2008,112(31):11 707
[16]Lu B,Li J G,Sakka Y.Science and Technology of Advanced Materials[J],2013,14(6):64 202
[17]Hu L F,Ma R Z,Ozawa T C et al.Angewandte Chemie International Edition[J],2009,48(21):3846
[18]Cai S,Lu B,Chen H B et al.Powder Technology[J],2017,317:224
[19]Wang Y,Lu B,Sun X D et al.Advances in Applied Ceramics[J],2011,110(2):95
[20]Lu B,Wang Y,Sun X D et al.Advances in Applied Ceramics[J],2012,111(7):389
[21]LüBin(吕滨),Sun Xudong(孙旭东),Sun Ting(孙挺)et al.Chinese Journal of Material Research(材料研究学报)[J],2011,25(3):255
[22]Jia M L,Zhang J H,Lu S Z et al.Chemical Physics Letters[J],2004,384(1-3):193
[23]Wu X L,Li J-G,Zhu Q et al.Dalton Transactions[J],2012,41(6):1854
[24]Thompson L C.Handbook on the Physics and Chemistry of Rare Earths[M].Netherlands:North-holland Physics,1979
[25]Cushing B L,Kolesnichenko V L,O’Connor C J.Chemical Reviews[J],2004,104(9):3893
[26]Jin Ye(金叶),Zhou Hongpeng(周虹鹏),Zhang Dingfei(张丁非).Rare Metal Materials and Engineering(稀有金属材料与工程)[J],2016,45(11):2790
[27]Pu Yong(蒲勇),Liu Bitao(刘碧桃),Zhu Dachuan(朱达川)et al.Rare Metal Materials and Engineering(稀有金属材料与工程)[J],2015,44(10):2529
[28]Wu Jiang(吴疆),Zhang Ping(张萍),Jiang Chundong(蒋春东)et al.Rare Metal Materials and Engineering(稀有金属材料与工程)[J],2016,45(4):1030
[29]Li J G,Li X D,Sun X D et al.Chemistry of Materials[J],2008,20(6):2274
[2]Gándara F,Perles J,Snejko N et al.Angewandte Chemie International Edition[J],2006,45(47):7998
[3]Geng F X,Matsushita Y,Ma R Z et al.Journal of the American Chemical Society[J],2008,130(48):16 344
[4]McIntyre L J,Jackson L K,Fogg A M.Chemistry of Materials[J],2008,20(1):335
[5]Lee K H,Byeon S H.European Journal of Inorganic Chemistry[J],2009(7):929
[6]Lee K H,Byeon S H.European Journal of Inorganic Chemistry[J],2009(31):4727
[7]Geng F X,Ma R Z,Sasaki T.Accounts of Chemical Research[J],2010,43(9):1177
[8]Zhao Y S,Li J G,Guo M X et al.Journal of Materials Chemistry C[J],2013,1(22):3584
[9]Lu B,Li J G,Suzuki T S et al.Journal of the American Ceramic Society[J],2015,98(5):1413
[10]Lu B,Li J G,Suzuki T S et al.Journal of the American Ceramic Society[J],2015,98(8):2480
[11]Lu B,Li J G,Sun X D et al.Journal of the American Ceramic Society[J],2015,98(12):3877
[12]Wakefield G,Holland E,Dobson P J et al.Advanced Materials[J],2001,13(20):1557
[13]Byeon S H,Ko M G,Park J C et al.Chemistry of Materials[J],2002,14(2):603
[14]Hirai T,Hirano T,Komasawa I.Journal of Materials Chemistry[J],2000,10(10):2306
[15]Li J G,Li X D,Sun X D et al.The Journal of Physical Chemistry C[J],2008,112(31):11 707
[16]Lu B,Li J G,Sakka Y.Science and Technology of Advanced Materials[J],2013,14(6):64 202
[17]Hu L F,Ma R Z,Ozawa T C et al.Angewandte Chemie International Edition[J],2009,48(21):3846
[18]Cai S,Lu B,Chen H B et al.Powder Technology[J],2017,317:224
[19]Wang Y,Lu B,Sun X D et al.Advances in Applied Ceramics[J],2011,110(2):95
[20]Lu B,Wang Y,Sun X D et al.Advances in Applied Ceramics[J],2012,111(7):389
[21]LüBin(吕滨),Sun Xudong(孙旭东),Sun Ting(孙挺)et al.Chinese Journal of Material Research(材料研究学报)[J],2011,25(3):255
[22]Jia M L,Zhang J H,Lu S Z et al.Chemical Physics Letters[J],2004,384(1-3):193
[23]Wu X L,Li J-G,Zhu Q et al.Dalton Transactions[J],2012,41(6):1854
[24]Thompson L C.Handbook on the Physics and Chemistry of Rare Earths[M].Netherlands:North-holland Physics,1979
[25]Cushing B L,Kolesnichenko V L,O’Connor C J.Chemical Reviews[J],2004,104(9):3893
[26]Jin Ye(金叶),Zhou Hongpeng(周虹鹏),Zhang Dingfei(张丁非).Rare Metal Materials and Engineering(稀有金属材料与工程)[J],2016,45(11):2790
[27]Pu Yong(蒲勇),Liu Bitao(刘碧桃),Zhu Dachuan(朱达川)et al.Rare Metal Materials and Engineering(稀有金属材料与工程)[J],2015,44(10):2529
[28]Wu Jiang(吴疆),Zhang Ping(张萍),Jiang Chundong(蒋春东)et al.Rare Metal Materials and Engineering(稀有金属材料与工程)[J],2016,45(4):1030
[29]Li J G,Li X D,Sun X D et al.Chemistry of Materials[J],2008,20(6):2274