镧系锗酸盐合成及应用的研究进展

摘要/Abstract

摘要： 稀土作为一种重要的战略资源,是高精尖产业中所需的关键原料之一。镧系锗酸盐作为稀土功能材料中的一种,具有与稀土化合物相似的4f电子结构和与硅酸盐类似的O-Ge四面体结构,同时具备稀土化合物和硅酸盐的物理化学性能与结构特征,受到国内外学者的广泛关注与研究。目前,镧系锗酸盐展现出较好的光学、电学、磁学以及铁电等物理化学性能,在相关领域有着较好的应用前景。文章综述了镧系锗酸盐合成方法及应用的研究现状,重点讨论了高温固相法、助熔剂法、水热合成法和络合法等制备方法,以及镧系锗酸盐在发光材料、光催化材料、固体电解质等领域的应用情况,同时对镧系锗酸盐制备技术的发展趋势和未来的应用领域进行了展望。

关键词: 稀土化合物, 镧系锗酸盐, 功能材料, 合成方法

Abstract: As an important strategic resource, rare earth is one of the key materials needed in high precision industry. Lanthanide germanate is a variety of rare earth functional materials, it has 4f electronic structure and O-Ge tetrahedral structure which are similar to rare earth functional materials and silicate. Lanthanide germanate also has the physical and chemical properties and structural characteristics of rare earth functional materials and silicate, which has received extensive concern and study at domestic and overseas. At the moment, lanthanide germanates show excellent physical and chemical properties such as optical, electrical, magnetic and ferroelectric properties, and have a better application prospect in related fields. In this paper, the synthesis methods and research status of lanthanide germanates were reviewed. The preparation of lanthanide germanates by high temperature solid method, flux method, hydrothermal synthesis method and complex method were discussed emphatically, the applications of lanthanide germanates in luminescent materials, photocatalytic materials and solid electrolyte were introduced. Then the development tread and application domain of lanthanide germanate preparation technology were prospected.

Key words: rare earth compound, lanthanide germanate, functional material, synthesis method

中图分类号:

O616.4

郝先东, 邱宏菊, 桂雨曦, 段利平, 陈菓, 高磊. 镧系锗酸盐合成及应用的研究进展[J]. 硅酸盐通报, 2021, 40(11): 3730-3739.

HAO Xiandong, QIU Hongju, GUI Yuxi, DUAN Liping, CHEN Guo, GAO Lei. Research Progress on Synthesis and Application of Lanthanide Germanates[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(11): 3730-3739.

参考文献

[1] COTTON S. Lanthanide and actinide chemistry[M]. Chichester, UK: John Wiley & Sons, Ltd, 2006.
[2] 佟嘉欣,邹鹏.NaLuF₄上转换发光材料的光学与温敏性质研究[J].科学技术创新,2021(1):35-36.
TONG J X, ZOU P. Optical and temperature-sensitive properties of NaLuF₄ up-conversion luminescent materials[J]. Scientific and Technological Innovation, 2021(1): 35-36 (in Chinese).
[3] 李允烨.射线屏蔽材料的研究进展及新型稀土/聚丙烯复合纤维材料的制备[D].北京:北京服装学院,2018.
LI Y Y. Research progress of radiation shielding materials and preparation of new rare earth/polypropylene composite fibers[D]. Beijing: Beijing Institute of Clothing Technology, 2018 (in Chinese).
[4] 赵伟,谌昀,胡强,等.稀土催化材料综述[J].江西科学,2021,39(1):1-7+24.
ZHAO W, CHEN Y, HU Q, et al. Brief overview of rare earth catalytic materials[J]. Jiangxi Science, 2021, 39(1): 1-7+24 (in Chinese).
[5] 杨佳鑫.AlH₃储氢材料的改性研究[D].合肥:中国科学技术大学,2020.
YANG J X. Study on the modification of AlH₃ hydrogen storage material[D]. Hefei: University of Science and Technology of China, 2020 (in Chinese).
[6] 杨文锋,刘颖,杨林,等.核辐射屏蔽材料的研究进展[J].材料导报,2007,21(5):82-85.
YANG W F, LIU Y, YANG L, et al. Research progress in shielding materials for nuclear radiation[J]. Materials Review, 2007, 21(5): 82-85 (in Chinese).
[7] ZHAO X G, WANG K, YAN T T, et al. Synthesis and pressure-induced reversible phase transition of a crystalline solid europium germanate NaEuGeO₄[J]. Chinese Journal of Chemistry, 2012, 30(9): 2066-2072.
[8] YIN G C, YIN H, SUN M L, et al. New approach to improve the conductivity of apatite-type lanthanum germanate La_9.33Ge₆O₂₆ as electrolyte for IT-SOFCs[J]. RSC Adv, 2014, 4(31): 15968-15974.
[9] CASCALES C, FERNÁNDEZ DÍAZ M T, MONGE M A. Low-temperature magnetic ordering in rare-earth copper germanates R₂CuGe₄O₁₂, R=Ho, Er[J]. Chemistry of Materials, 2000, 12(11): 3369-3375.
[10] CASCALES C, FERNÁNDEZ-DÍAZ M T, MONGE M A, et al. Crystal structure and low-temperature magnetic ordering in rare earth iron germanates RFeGe₂O₇, R=Y, Pr, Dy, Tm, and Yb[J]. Chemistry of Materials, 2002, 14(5): 1995-2003.
[11] MOORE E E, KOCEVSKI V, JUILLERAT C A, et al. Understanding the stability of salt-inclusion phases for nuclear waste-forms through volume-based thermodynamics[J]. Scientific Reports, 2018, 8: 15294.
[12] JANA S, GHOSH D, WANKLYN B M. Magnetic susceptibilities and anisotropy studies of holmium pyrogermanate (Ho₂Ge₂O₇) crystal[J]. Journal of Magnetism and Magnetic Materials, 1998, 183(1/2): 135-142.
[13] 尹广超.磷灰石结构硅/锗酸镧电解质材料的制备与性能研究[D].长春:吉林大学,2014.
YIN G C. Synthesis and characterization of apatite-type lanthanum silicates/germanates materials as electrolyte[D]. Changchun: Jilin University, 2014 (in Chinese).
[14] LALENA J N, CLEARY D A, CARPENTER E E, et al. Inorganic materials synthesis and fabrication[M]. Hoboken, NJ, USA: John Wiley & Sons, Inc, 2008.
[15] SCHWARZ J A, CONTESCU C, CONTESCU A. Methods for preparation of catalytic materials[J]. Chemical Reviews, 1995, 95(3): 477-510.
[16] RAO C N R, BISWAS K. Essentials of inorganic materials synthesis[M]. Hoboken, NJ: John Wiley & Sons, Inc, 2015.
[17] TAVIOT-GUÉHO C, LÉONE P, PALVADEAU P, et al. Synthesis and structural characterization of two new rare-earth manganese germanates: CeMn₂Ge₄O₁₂ and GdMnGe₂O₇[J]. Journal of Solid State Chemistry, 1999, 143(2): 145-150.
[18] XU D, AVDEEV M, BATTLE P D, et al. Magnetic properties of CeMn_2-xCo_xGe₄O₁₂ (0≤x≤2) as a function of temperature and magnetic field[J]. Inorganic Chemistry, 2017, 56(5): 2750-2762.
[19] SHARMA C, SINGH K L, SINGH A P, et al. Microwave and conventional processing of niobium and manganese doped lanthanum germanate based apatites[J]. Materials Chemistry and Physics, 2018, 218: 204-209.
[20] 朱凤霞,易健宏,周承商,等.微波烧结对粉末冶金铜材显微组织与性能的影响[J].粉末冶金材料科学与工程,2007,12(6):364-368.
ZHU F X, YI J H, ZHOU C S, et al. Influence of microwave sintering on microstructures and properties of copper powder metallurgy material[J]. Materials Science and Engineering of Powder Metallurgy, 2007, 12(6): 364-368 (in Chinese).
[21] 廖佳.微波烧结和玻璃渗透制备3Y-TZP全瓷材料的研究[D].南昌:南昌航空大学,2014.
LIAO J. The study of 3Y-TZP all-ceramic materials prepared by microwave sintering and glass infiltration[D]. Nanchang: Nanchang Hangkong University, 2014 (in Chinese).
[22] 李月明,黄丹,廖润华,等.熔盐法合成晶体的研究现状与进展[J].陶瓷学报,2008,29(2):164-169.
LI Y M, HUANG D, LIAO R H, et al. Development of crystal synthesis by molten salt method[J]. Journal of Ceramics, 2008, 29(2): 164-169 (in Chinese).
[23] YIN G C, YIN H, WANG X, et al. Subtle high-pressure behaviors of apatite-type La_9.33Ge₆O₂₆[J]. Journal of Alloys and Compounds, 2018, 735: 750-755.
[24] HUGHEY K, YEON J, ZUR LOYE H C. Crystal growth and structure determination of the new neodymium germanate, Na₂NdGeO₄(OH)[J]. Journal of Chemical Crystallography, 2014, 44(6): 320-323.
[25] CAMPÁ J A, CASCALES C, GUTIÉRREZ-PUEBLA E, et al. CuYb₂Ge₄O₁₂, a new bidimensionally tunneled structure[J]. Journal of Solid State Chemistry, 1996, 124(1): 17-23.
[26] CHEN P L, CHIANG P Y, YEH H C, et al. Synthesis, crystal structure, magnetic and luminescence properties of KEuGe₂O₆: a europium cyclogermanate containing infinite chains of edge-sharing Eu-O polyhedra[J]. Dalton Transactions (Cambridge, England), 2008(13): 1721-1726.
[27] DEMIANETS L N, LOBACHEV A N, EMELCHENKO G A. Rare-earth germanates[M]//Crystals. Berlin, Heidelberg: Springer Berlin Heidelberg, 1980: 101-144.
[28] GUPTA S K, MAO Y B. Recent developments on molten salt synthesis of inorganic nanomaterials: a review[J]. The Journal of Physical Chemistry C, 2021, 125(12): 6508-6533.
[29] ANANIAS D, ALMEIDA PAZ F A, CARLOS L D, et al. Rare-earth germanate visible, near-infrared, and up-conversion emitters[J]. European Journal of Inorganic Chemistry, 2018, 2018(20/21): 2444-2451.
[30] FULLE K, SANJEEWA L D, MCMILLEN C D, et al. One-pot hydrothermal synthesis of Tb^III₁₃(GeO₄)₆O₇(OH) and K₂Tb^IVGe₂O₇: preparation of a stable terbium (4+) complex[J]. Inorganic Chemistry, 2017, 56(11): 6044-6047.
[31] SANJEEWA L, ROSS K A, SARKIS C L, et al. Single crystals of cubic rare-earth pyrochlore germanates: RE₂Ge₂O₇ (RE=Yb and Lu) grown by a high-temperature hydrothermal technique[J]. Inorganic Chemistry, 2018, 57(20): 12456-12460.
[32] LIPINA O A, SURAT L L, MELKOZEROVA M A, et al. Synthesis, crystal structure and luminescence properties of CaY_2-xEu_xGe₃O₁₀ (x=0-2)[J]. Journal of Solid State Chemistry, 2013, 206: 117-121.
[33] LIPINA O A, SURAT L L, TYUTYUNNIK A P, et al. Synthesis and structural study of a new group of trigermanates, CaRE₂Ge₃O₁₀(RE=La-Yb)[J]. CrystEngComm, 2015, 17(17): 3333-3344.
[34] LIPINA O A, MELKOZEROVA M A, CHUFAROV A Y, et al. Structure-luminescence relationship in Eu³⁺-doped Sr₃La₂(Ge₃O₉)₂ phosphors[J]. Optical Materials, 2019, 87: 145-150.
[35] LIPINA O A, BAKLANOVA Y V, SURAT L L, et al. Structural and optical characterization of Tm³⁺-doped apatite related NaLa₉(GeO₄)₆O₂ phosphors[J]. Ceramics International, 2020, 46(16): 26416-26424.
[36] 王伟.稀土上转换发光材料的研究与应用[J].广州化工,2014,42(11):32-34.
WANG W. Research and application of rare earth up conversion luminescent materials[J]. Guangzhou Chemical Industry, 2014, 42(11): 32-34 (in Chinese).
[37] 冷静.稀土离子掺杂硅酸盐发光材料的制备及发光特性研究[D].大连:大连海事大学,2017.
LENG J. Preparation and luminescence properties of rare earth ions doped silicate luminescent materials[D]. Dalian: Dalian Maritime University, 2017 (in Chinese).
[38] BAKLANOVA Y V, LIPINA O A, ENYASHIN A N, et al. Nd³⁺, Ho³⁺-codoped apatite-related NaLa₉(GeO₄)₆O₂ phosphors for the near- and middle-infrared region[J]. Dalton Transactions, 2018, 47(39): 14041-14051.
[39] WANG X, WANG Y, LIU Q, et al. K₃[Tb_xEu_1-xGe₃O₈(OH)₂] (x=1, 0.88, 0.67, 0): 2D-layered lanthanide germanates with tunable photoluminescent properties[J]. Inorganic Chemistry, 2012, 51(8): 4779-4783.
[40] 石双欣,卫静.光催化技术处理染料废水研究进展[J].绿色科技,2021,23(2):63-65.
SHI S X, WEI J. Research progress in the treatment of dye wastewater by photocatalytic technology[J]. Journal of Green Science and Technology, 2021, 23(2): 63-65 (in Chinese).
[41] PEI L Z, WANG S, JIANG Y X, et al. Single crystalline Sr germanate nanowires and their photocatalytic performance for the degradation of methyl blue[J]. CrystEngComm, 2013, 15(38): 7815.
[42] ZHANG J H, HAO X D, WANG X, et al. Synthesis, structure, and characterization of RbNdGe₂O₆ as a novel visible-light-driven catalyst for photodegradation methylene blue[J]. Journal of Solid State Chemistry, 2020, 285: 121246.
[43] 王泽岩,王朋,刘媛媛,等.基于晶体学原理的高效光催化材料的设计与制备[J].人工晶体学报,2021,50(4):685-707.
WANG Z Y, WANG P, LIU Y Y, et al. Design and synthesis of efficient photocatalyst based on the principal of crystallography[J]. Journal of Synthetic Crystals, 2021, 50(4): 685-707 (in Chinese).
[44] 韩作良.La_9.33Ge₆O₂₆电解质材料制备及其Ge位Co掺杂的研究[D].长春:吉林大学,2017.
HAN Z L. Synthesis and characterization of La_9.33Ge₆O₂₆ electrolyte and its Co doping on Ge site[D]. Changchun: Jilin University, 2017 (in Chinese).
[45] 谢晓君.锗酸镧基陶瓷电解质的制备与表征[D].长春:吉林大学,2014.
XIE X J. The synthesis and characterization of lanthanum germanate-based as ceramic electrolyte[D]. Changchun: Jilin University, 2014 (in Chinese).
[46] LI H N, BAIKIE T, PRAMANA S S, et al. Synthesis and characterisation of vanadium doped alkaline earth lanthanum germanate oxyapatite electrolyte[J]. Journal of Materials Chemistry, 2012, 22(6): 2658-2669.
[47] KENDRICK E, ORERA A, SLATER P R. Neutron diffraction structural study of the apatite-type oxide ion conductor, La₈Y₂Ge₆O₂₇: location of the interstitial oxide ion site[J]. Journal of Materials Chemistry, 2009, 19(42): 7955.
[48] LEÓN-REINA L, MARTÍN-SEDEO M C, LOSILLA E R, et al. Crystalchemistry and oxide ion conductivity in the lanthanum oxygermanate apatite series[J]. Chemistry of Materials, 2003, 15(10): 2099-2108.
[49] LEÓN-REINA L, LOSILLA E R, MARTÍNEZ-LARA M, et al. Interstitial oxygen in oxygen-stoichiometric apatites[J]. Journal of Materials Chemistry, 2005, 15(25): 2489.
[50] LEÓN-REINA L, LOSILLA E R, MARTÍNEZ-LARA M, et al. Interstitial oxygen conduction in lanthanum oxy-apatite electrolytes[J]. Journal of Materials Chemistry, 2004, 14(7): 1142-1149.
[51] ABRAM E J, KIRK C A, SINCLAIR D C, et al. Synthesis and characterisation of lanthanum germanate-based apatite phases[J]. Solid State Ionics, 2005, 176(23/24): 1941-1947.
[52] LEÓN-REINA L, PORRAS-VÁZQUEZ J M, LOSILLA E R, et al. Phase transition and mixed oxide-proton conductivity in germanium oxy-apatites[J]. Journal of Solid State Chemistry, 2007, 180(4): 1250-1258.
[53] SANSOM J E H, SLATER P R. Oxide ion conductivity in the mixed Si/Ge apatite-type phases La_9.33Si_6-xGe_xO₂₆[J]. Solid State Ionics, 2004, 167(1/2): 23-27.
[54] SANSOM J E H, NAJIB A, SLATER P R. Oxide ion conductivity in mixed Si/Ge-based apatite-type systems[J]. Solid State Ionics, 2004, 175(1/2/3/4): 353-355.
[55] SANSOM J E H, SERMON P A, SLATER P R. Synthesis and conductivities of the Ti doped apatite-type phases (La/Ba)_10-x(Si/Ge)_6-yTi_yO_26+z[J]. Solid State Ionics, 2005, 176(19/20/21/22): 1765-1768.
[56] SANSOM J E H, KENDRICK E, TOLCHARD J R, et al. A comparison of the effect of rare earth vs Si site doping on the conductivities of apatite-type rare earth silicates[J]. Journal of Solid State Electrochemistry, 2006, 10(8): 562-568.
[57] TOLCHARD J R, SANSOM J E H, SLATER P R, et al. Effect of Ba and Bi doping on the synthesis and sintering of Ge-based apatite phases[J]. Journal of Solid State Electrochemistry, 2004, 8(9): 668-673.