通过开环易位聚合制备的基于三联吡啶的二氧化硅载体用于贵金属的选择性萃取。

Terpyridine-based silica supports prepared by ring-opening metathesis polymerization for the selective extraction of noble metals.

作者信息

Glatz Ines, Mayr Monika, Hoogenboom Richard, Schubert Ulrich S, Buchmeiser Michael R

机构信息

Institut für Analytische Chemie und Radiochemie, Universität Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria.

出版信息

J Chromatogr A. 2003 Oct 10;1015(1-2):65-71. doi: 10.1016/s0021-9673(03)01283-4.

DOI:10.1016/s0021-9673(03)01283-4

PMID:14570320

Abstract

The synthesis of a terpyridine-based sorbent for solid-phase extraction (SPE) of noble metal ions is described. For this purpose, 4'-(norborn-2-en-5-ylmethylenoxy)terpyridine was copolymerized with norborn-2-ene via Mo(N-2,6-i-Pr2-C6H3)(=CHCMe2Ph) (OC(CH3)(CF3)2)2-catalyzed ring-opening metathesis polymerization (ROMP) to give a poly(norbornene900(-b-4'-(norborn-2-en-5-ylmethylenoxy)terpyridine60) block-copolymer. This block-copolymer was used for the preparation of polymer-coated silica 60 (4.8 wt.% coating), which was investigated for its extraction capabilities for Cr(III), Mn(II), Re(II), Fe(III), Ru(III), Co(II), Rh(III), Ir(III), Ni(II), Pd(II), Pt(II), Cu(II), Ag(I), Au(III), Zn(II), Cd(II) and Hg(II), at different pH. Under competitive conditions and at pH < 0.6, the selectivity order was Pd approximately = Ag approximately = Au approximately = Pt > Re > Ir > Rh > Ru > Fe > Cr approximately = Mn approximately = Cd approximately = Zn. Enhanced selectivity was observed at pH = 3.5, the order was Au > Hg > Pd approximately = Ag > Rh > Pt > Ir approximately = Re > Cu > Co approximately = Zn approximately = Cd approximately = Ni > Cr > Mn. The maximum metal loading that was achieved under non-competitive conditions was > 6 mg/g for Au(III), Hg(II), Pd(II) and Ag(I). Even under competitive conditions, loadings of > 6 mg/g were realized for Au(III) and Hg(II). Quantitative recoveries > 97% were observed for all metals in case loading was stopped before reaching the point of breakthrough.

摘要

描述了一种用于贵金属离子固相萃取（SPE）的基于三联吡啶的吸附剂的合成。为此，通过Mo(N-2,6-二异丙基-苯基)(=CHCMe2Ph)(OC(CH3)(CF3)2)2催化的开环易位聚合（ROMP），将4'-(降冰片-2-烯-5-基亚甲基氧基)三联吡啶与降冰片-2-烯共聚，得到聚（降冰片烯900(-b-4'-(降冰片-2-烯-5-基亚甲基氧基)三联吡啶60）嵌段共聚物。该嵌段共聚物用于制备聚合物包覆的硅胶60（涂层含量为4.8 wt.%），研究了其在不同pH值下对Cr(III)、Mn(II)、Re(II)、Fe(III)、Ru(III)、Co(II)、Rh(III)、Ir(III)、Ni(II)、Pd(II)、Pt(II)、Cu(II)、Ag(I)、Au(III)、Zn(II)、Cd(II)和Hg(II)的萃取能力。在竞争条件下且pH < 0.6时，选择性顺序为Pd≈Ag≈Au≈Pt > Re > Ir > Rh > Ru > Fe > Cr≈Mn≈Cd≈Zn。在pH = 3.5时观察到选择性增强，顺序为Au > Hg > Pd≈Ag > Rh > Pt > Ir≈Re > Cu > Co≈Zn≈Cd≈Ni > Cr > Mn。在非竞争条件下，Au(III)、Hg(II)、Pd(II)和Ag(I)实现的最大金属负载量> 6 mg/g。即使在竞争条件下，Au(III)和Hg(II)的负载量也> 6 mg/g。如果在达到穿透点之前停止负载，所有金属的定量回收率均> 97%。