Selective isolation of gold facilitated by second-sphere coordination with α-cyclodextrin.

Selective isolation of gold facilitated by second-sphere coordination with α-cyclodextrin.
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DOI:
10.1038/ncomms2891
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发表时间:
2013
影响因子:
16.6
通讯作者:
--
中科院分区:
综合性期刊1区
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--
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从环境的角度来看,使用环境友好的化学方法进行黄金回收势在必行。本文报道了在α-环糊精和KauBr_4在水中快速共沉淀过程中,形成的一维超分子配合物与延伸的{[K(OH_2)_6][AuBr_4](α-环糊精)_2}_n超结构链的自发组装。这种相变对于这种金盐是选择性的,即使在存在其他正方形平面钯和铂络合物的情况下也是如此。通过对α-、β-和γ-环糊精与KAuBr 4和KAuCl 4之间的六种包合物的单晶X射线分析,我们假设α-环糊精和[AuBr 4]−之间分子识别的完美匹配导致离子相对于α-环糊精通道的近轴取向,这有助于涉及[AuBr 4]−和[K(OH 2)6]+的高度特异性的第二球配位,并驱动1:2加合物的共沉淀。这一发现预示着一个绿色的主-客体过程,利用α-环糊精-一种廉价和环境友好的碳水化合物从含金原料中回收金。 目前,从废料中回收黄金需要无机氰化物,需要更环保的方法。在这里,作者报告说,α-环糊精和金之间的主客体相互作用导致一维超结构的沉淀,提供了一种选择性和绿色的替代方案。
Gold recovery using environmentally benign chemistry is imperative from an environmental perspective. Here we report the spontaneous assembly of a one-dimensional supramolecular complex with an extended {[K(OH2)6][AuBr4](α-cyclodextrin)2}n chain superstructure formed during the rapid co-precipitation of α-cyclodextrin and KAuBr4 in water. This phase change is selective for this gold salt, even in the presence of other square-planar palladium and platinum complexes. From single-crystal X-ray analyses of six inclusion complexes between α-, β- and γ-cyclodextrins with KAuBr4 and KAuCl4, we hypothesize that a perfect match in molecular recognition between α-cyclodextrin and [AuBr4]− leads to a near-axial orientation of the ion with respect to the α-cyclodextrin channel, which facilitates a highly specific second-sphere coordination involving [AuBr4]− and [K(OH2)6]+ and drives the co-precipitation of the 1:2 adduct. This discovery heralds a green host–guest procedure for gold recovery from gold-bearing raw materials making use of α-cyclodextrin—an inexpensive and environmentally benign carbohydrate. Currently, gold recovery from waste materials requires inorganic cyanides and more environmentally benign methods are required. Here, the authors report that host–guest interactions between α-cyclodextrin and gold lead to the precipitation of one-dimensional superstructures, offering a selective and green alternative.
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