Selective Gold Recovery and Catalysis in a Highly Flexible Methionine-Decorated Metal–Organic Framework

Abstract

A novel chiral 3D bioMOF exhibiting functional channels with thio-alkyl chains derived from the natural amino acid l-methionine (1) has been rationally prepared. The well-known strong affinity of gold for sulfur derivatives, together with the extremely high flexibility of the thioether "arms" decorating the channels, account for a selective capture of gold(III) and gold(I) salts in the presence of other metal cations typically found in electronic wastes. The X-ray single-crystal structures of the different gold adsorbates Au(III)@1 and Au(I)@1 suggest that the selective metal capture occurs in a metal ion recognition process somehow mimicking what happens in biological systems and protein receptors. Both Au(III)@1 and Au(I)@1 display high activity as heterogeneous catalyst for the hydroalkoxylation of alkynes, further expanding the application of these novel hybrid materials.

Fine-tuning of the confined space in microporous metal–organic frameworks for efficient mercury removal

“…1). We report the synthesis and characterization of this novel three-dimensional bioMOF, 45,46 prepared from an oxamidato-based ligand 42,47,48 derived from the natural amino acid methionine, of formula {Cu…”

Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF

“…[34] MOFs could thus also find application as vessels encapsulating biological systems. [35] Among the large class of MOFs,b ioMOFs, [36] designed from naturally occurring organic ligands,are highly promising for both mercury removal and biomimicry.Inthis context, we have recently reported ar obust and water-stable,h eterobimetallic calcium(II)/copper(II) three-dimensional (3D) bioMOF, [37] which was synthesized by using the enantiopure bis[(S)-methionine]oxalyl diamide [37][38][39][40] ligand derived from the natural amino acid l-methionine (see the Supporting Information, Scheme S1). This porous material with the formula {Ca II Cu II 6 [(S,S)-methox] 3 (OH) 2 (H 2 O)}·16 H 2 O( 1) features functional channels decorated with thioalkyl chains, which account for its strong and selective affinity for different gold salts as well as excellent catalytic activity.…”

“…[35] Among the large class of MOFs,b ioMOFs, [36] designed from naturally occurring organic ligands,are highly promising for both mercury removal and biomimicry.Inthis context, we have recently reported ar obust and water-stable,h eterobimetallic calcium(II)/copper(II) three-dimensional (3D) bioMOF, [37] which was synthesized by using the enantiopure bis[(S)-methionine]oxalyl diamide [37][38][39][40] ligand derived from the natural amino acid l-methionine (see the Supporting Information, Scheme S1). [37] On the basis of the well-known affinity of mercury for sulfur atoms,w e have further extended this work to evaluate the efficiency of 1 in the capture and removal of Hg 2+ and CH 3 Hg + from aqueous media (Scheme S2). [37] On the basis of the well-known affinity of mercury for sulfur atoms,w e have further extended this work to evaluate the efficiency of 1 in the capture and removal of Hg 2+ and CH 3 Hg + from aqueous media (Scheme S2).…”

Au3+/Au0 Supported on Chromium(III) Terephthalate Metal Organic Framework (MIL-101) as an Efficient Heterogeneous Catalystfor Three-Component Coupling Synthesis of Propargylamines

“…In the present study, the MIL-101 was synthesized in deionized water, without the addition of toxic and corrosive hydrofluoric acid that is typically used in the standard preparation of MIL-101 [49]. MIL-101 was hydrothermally synthesized at 220 °C for 18 h using chromium(III) nitrate nonahydrate (Cr(NO 3 ) 3 ∙9H 2 O), terephthalic acid, and water [28,50,51,52]. The as-synthesized MIL-101 was further purified using hot ethanol under reflux to remove the remaining unreacted ligands trapped in the pores.…”

“…MOFs have attracted considerable attention because of their enormous varieties of interesting molecular topologies and wide potential applications as functional materials [18,19,20,21,22,23,24,25,26,27,28]. In recent years, numerous studies have focused on the heterogenization of homogeneous catalysts based on MOFs [29,30,31,32,33,34].…”