Nakajima Akira
Department of Chemistry, Miyazaki Medical College, Kiyotake, Miyazaki 889-1692, Japan.
Talanta. 2002 May 24;57(3):537-44. doi: 10.1016/s0039-9140(02)00068-1.
The persimmon tannin gel can adsorb vanadium highly effectively from aqueous solutions containing VOCl(2) and NH(4)VO(3), respectively. The adsorption of vanadium from the VOCl(2) solution had a broad maximum at around pH 5-6, while that from the NH(4)VO(3) solution, a sharp maximum at around pH 3.75 and a broad one at around pH 5-6. The adsorption of vanadium by the gel from both VOCl(2) and NH(4)VO(3) solutions was rapid, and was obeyed the Langmuir adsorption isotherm. The ESR spectrum of VO(2+) in the persimmon tannin gel showed a typical powder pattern with g-anisotropy and anisotropic hyperfine structure (I=7/2), with g(//)=1.937, g( perpendicular)=2.005, mid R:A(//)mid R:=552 MHz, and mid R:A( perpendicular)mid R:=168 MHz, suggesting a square pyramidal coordination structure of VO(2+)-persimmon tannin complex. The ESR analysis of vanadium adsorption from the NH(4)VO(3) solution (pH 6) indicated the reduction of VO(3)(-) to VO(2+). The high vanadium-adsorption ability of the persimmon tannin gel from the VOCl(2) solution was attributed to the stable complex formation of VO(2+) with catechol and pyrogallol groups in the gel, while the vanadium adsorption from the NH(4)VO(3) solution can be explained as the combination of H(3)VO(4) and VO(2+) adsorptions.
柿单宁凝胶能分别从含有VOCl₂和NH₄VO₃的水溶液中高效吸附钒。从VOCl₂溶液中吸附钒在pH 5 - 6左右有一个较宽的最大值,而从NH₄VO₃溶液中吸附钒,在pH 3.75左右有一个尖锐的最大值,在pH 5 - 6左右有一个较宽的最大值。凝胶对VOCl₂和NH₄VO₃溶液中钒的吸附都很快,且符合朗缪尔吸附等温线。柿单宁凝胶中VO²⁺的电子自旋共振(ESR)谱显示出具有g-各向异性和各向异性超精细结构(I = 7/2)的典型粉末图谱,g(//)=1.937,g(⊥)=2.005,中间R:A(//)中间R:=552 MHz,中间R:A(⊥)中间R:=168 MHz,表明VO²⁺ - 柿单宁络合物具有四方锥配位结构。对从NH₄VO₃溶液(pH 6)中吸附钒的ESR分析表明VO₃⁻还原为VO²⁺。柿单宁凝胶对VOCl₂溶液中钒的高吸附能力归因于凝胶中VO²⁺与儿茶酚和邻苯三酚基团形成稳定的络合物,而从NH₄VO₃溶液中吸附钒可解释为H₃VO₄和VO²⁺吸附的结合。