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塩挿入鉱物変換法による粘土鉱物の光触媒化

Synthesis of photocatalytic minerals by clay mineral salt insertion method

杉田 剛   ; 森 勝伸*; 下山 巖   

Sugita, Tsuyoshi; Mori, Masanobu*; Shimoyama, Iwao

本研究では、粘土鉱物のサブグループである黒雲母をCaCl$$_{2}$$で熱処理することにより、光触媒に変換することを検討した。得られた反応生成物の組成、構造、光学特性、およびCrVIとサリチル酸(SA)に対する光触媒活性を分析した。黒雲母とCaCl$$_{2}$$の混合物は黒雲母の結晶構造を保持したまま600$$^{circ}$$Cまで加熱できたが、700$$^{circ}$$Cまで加熱すると八面体のワダライト結晶に変化した。熱処理後に得られたワダライトのバンドギャップは約3.10eVであった。単位表面積あたりの光触媒還元率は熱処理温度の上昇とともに著しく増加し、800$$^{circ}$$Cで焼成した試料のCrVI還元率は500$$^{circ}$$Cで焼成した試料の約18倍、SA分解率は約9倍であった。反応生成物の溶出試験では、Ca$$^{2+}$$とCl$$^{-}$$の溶出が特に顕著であった。熱処理後に黒雲母構造を保持した試料でも光触媒活性を示したことから、この方法は雲母や類似の構造を持つ関連鉱物から光触媒を調製するのに応用できる可能性がある。

This study investigates the conversion of biotite, a subgroup of clay minerals, into photocatalysts through heat treatment with CaCl$$_{2}$$. The resulting reaction products were analyzed in terms of their composition, structure, optical properties, and photocatalytic activity against Cr(VI) and salicylic acid (SA). Biotite and CaCl$$_{2}$$ mixtures could be heated to 600$$^{circ}$$C while retaining the biotite crystal structure, whereas heating to 700$$^{circ}$$C resulted in transformation to octahedral wadalite crystals. The band gap of the wadalite obtained after heat treatment was approximately 3.10 eV. The photocatalytic reduction rate per unit surface area increased markedly with increasing heat-treatment temperature, and the Cr(VI) reduction and SA degradation rates of the sample calcined at 800$$^{circ}$$C were approximately 18 and 9 times greater, respectively, than those of the sample calcined at 500$$^{circ}$$C. Leaching tests of the reaction products revealed that the elution of Ca$$^{2+}$$ and Cl$$^{-}$$ was particularly significant. Even the samples that retained the biotite structure after heat treatment displayed some photocatalytic activity, indicating that this method may be applicable to preparing photocatalysts from mica and related minerals with similar structures.

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