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非晶态磷酸钛及二氧化硅改性磷酸钛的合成、表征与吸附性能

Synthesis, characterization, and sorption properties of amorphous titanium phosphate and silica-modified titanium phosphates.

作者信息

Maslova Marina V, Rusanova Daniela, Naydenov Valeri, Antzutkin Oleg N, Gerasimova Lidia G

机构信息

Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, Kola Science Center, Russian Academy of Sciences, Fersman st. 26a, Apatity, Murmansk region, 184209 Russia.

出版信息

Inorg Chem. 2008 Dec 1;47(23):11351-60. doi: 10.1021/ic801274z.

Abstract

Amorphous titanium hydroxyphosphate with formula Ti(OH)(1.36)(HPO(4))(1.32).2.3H(2)O and a new silica-modified titanium hydroxyphosphate with a general formula Ti(OH)(2x)(HPO(4))(2-x).ySiO(2).nH(2)O are synthesized and characterized using IR, TG, XRD, SEM, solid-state NMR, and BET techniques. It is concluded that SiO(2) is evenly distributed within the titanium phosphate (TiP) agglomerates and that neither the separate silica phase nor the titanium silicates are formed during the synthesis of silica-modified titanium hydroxyphosphate. Correlations between the texture, ion-exchange properties of the amorphous titanium hydroxyphosphate, and the amount of SiO(2) present within the TiP matrix are established. Sorption properties of silica-modified titanium hydroxyphosphate toward Cs(+) and Sr(2+) are studied in a series of samples with an increasing amount of silica, at different pH, and in NaCl solutions with a varying ionic strength. It is found that sorption of Cs(+) does not depend practically on the amount of SiO(2) present, whereas the Sr(2+) uptake drastically decreases with an increase of silica amount. The effects of pH and of the electrolyte concentration on the sorption behavior of titanium phosphate are discussed in terms of ionic hydration shell and titanium phosphate structural specificity. The kinetics of sorption processes is also investigated, and the diffusion coefficients for cesium and strontium are obtained.

摘要

合成了化学式为Ti(OH)(1.36)(HPO(4))(1.32).2.3H(2)O的非晶态钛羟基磷酸盐以及通式为Ti(OH)(2x)(HPO(4))(2 - x).ySiO(2).nH(2)O的新型二氧化硅改性钛羟基磷酸盐,并采用红外光谱(IR)、热重分析(TG)、X射线衍射(XRD)、扫描电子显微镜(SEM)、固态核磁共振(NMR)和比表面积测定(BET)技术对其进行了表征。得出的结论是,SiO(2)均匀分布在磷酸钛(TiP)团聚体中,并且在二氧化硅改性钛羟基磷酸盐的合成过程中既没有形成单独的二氧化硅相也没有形成钛硅酸盐。建立了非晶态钛羟基磷酸盐的织构、离子交换性能与TiP基体中SiO(2)含量之间的相关性。在一系列二氧化硅含量不断增加、不同pH值以及不同离子强度的氯化钠溶液的样品中,研究了二氧化硅改性钛羟基磷酸盐对Cs(+)和Sr(2+)的吸附性能。发现Cs(+)的吸附实际上不依赖于SiO(2)的含量,而Sr(2+)的吸附量随着二氧化硅含量的增加而急剧下降。从离子水化层和磷酸钛的结构特异性方面讨论了pH值和电解质浓度对磷酸钛吸附行为的影响。还研究了吸附过程的动力学,并获得了铯和锶的扩散系数。

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