Sone Atsushi, Saito Tsuguyuki, Isogai Akira
Department of Biomaterials Science, Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo 113-8657, Japan.
Research and Development Center, Manufactured Products Development Laboratory, ZEON Co., 1-2-1 Yako, Kawasaki-ku, Kawasaki, Kanagawa 210-9507, Japan.
ACS Macro Lett. 2016 Dec 20;5(12):1402-1405. doi: 10.1021/acsmacrolett.6b00786. Epub 2016 Dec 8.
2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with sodium carboxylate groups (TOCN-Na) were nanodispersed in water. The Na ions of TOCN-Na were exchanged with other monovalent, divalent, and trivalent metal (M) ions. When an aqueous metal acetate or AlCl solution was added to a 0.1% TOCN-Na/water dispersion or TOCN-COOH gel/water mixture under suitable conditions followed by sonication in water, individually nanodispersed TOCNs-M with divalent and trivalent metal counterions were obtained in yields of 24-87%. The amount of metal introduced into TOCN-M was approximately 20-50% of the TOCN carboxylate content when divalent and trivalent metal ions were used. These results indicate that intrafibrillar ionic linkages are selectively formed and these TOCN-M species nanodisperse at the individual nanofiber level without agglomeration in water. Filter papers with adsorbed TOCN-Cu/water and TOCN-Ag/water dispersions efficiently decomposed or adsorbed HS and CHSH gases, but filter papers containing fibrous TEMPO-oxidized celluloses with Ag or Cu counterions had much lower gas-decomposition efficiencies.
带有羧酸钠基团的2,2,6,6-四甲基哌啶-1-氧基（TEMPO）氧化纤维素纳米原纤维（TOCN-Na）在水中呈纳米分散状态。TOCN-Na中的钠离子与其他单价、二价和三价金属（M）离子进行了交换。在合适的条件下，当将金属乙酸盐水溶液或AlCl溶液添加到0.1%的TOCN-Na/水分散液或TOCN-COOH凝胶/水混合物中，随后在水中进行超声处理时，分别获得了带有二价和三价金属抗衡离子的纳米分散的TOCN-M，产率为24 - 87%。当使用二价和三价金属离子时，引入到TOCN-M中的金属量约为TOCN羧酸盐含量的20 - 50%。这些结果表明，在纳米原纤维内部选择性地形成了离子键，并且这些TOCN-M物种在水中以单个纳米纤维水平进行纳米分散而不发生团聚。吸附有TOCN-Cu/水和TOCN-Ag/水分散液的滤纸能够有效地分解或吸附H₂S和CH₃SH气体，但是含有带有Ag或Cu抗衡离子的纤维状TEMPO氧化纤维素的滤纸的气体分解效率要低得多。
