Selective Gold Extraction from E-waste Leachate via Sulfur-Redox Mechanisms Using Sulfhydryl-Functionalized MOFs

Urban mining of precious metals from electronic waste (e-waste) offers a dual advantage by addressing solid waste management challenges and supplying high-value metals for diverse applications. However, traditional extraction methods generally suffer from poor selectivity and limited capacity in complex acidic leachate. Herein, we present a sulfhydryl-functionalized zirconium-based metal-organic framework (Zr-MSA-AA) as a recyclable and highly selective adsorbent for efficient gold recovery. Specifically, the Zr-MSA-AA exhibits high recovery capacity (1021 mg g^-1), remarkable pH-universal, and superb selectivity (K_d of 2.2 × 10⁷ mL g^-1) for gold ions across wide pH range and competitive conditions. Comprehensive mechanistic investigations highlight the pivotal role of sulfhydryl groups in selectively capturing gold ions. The redox-transformation of sulfhydryl and sulfonic acid groups mediated the reduction of Au(III) to Au(0) through the nucleation of chlorine-stabilized gold clusters. This unique mechanism, driven by the redox activity of designed sulfhydryl sites, not only mitigates interference from competing cations but also facilitates rapid adsorption kinetics (k_f of 1.17 × 10^-7 m s^-1) for gold ions, surpassing the performance of previous adsorbents. Consequently, Zr-MSA-AA demonstrates exceptional practical applicability, achieving high-purity gold recovery (23.8 Karat) from real e-waste leachate through straightforward physical separation methods. This study introduces an alternative practical strategy for utilizing sulfur's redox activity in adsorbent design, advancing the sustainable recycling of non-renewable metal resources while contributing to environmental conservation.