Unraveling the Role of Solvation and Ion Valency on Redox-Mediated Electrosorption through In Situ Neutron Reflectometry and Ab Initio Molecular Dynamics

JACS Au, Journal Year: 2024, Volume and Issue: 4(3), P. 919 - 929

Published: Feb. 1, 2024

Solvation and ion valency effects on selectivity of metal oxyanions at redox–polymer interfaces are explored through in situ spatial-temporally resolved neutron reflectometry combined with large scale ab initio molecular dynamics. The ReO4– vs MoO42– for two redox-metallopolymers, poly(vinyl ferrocene) (PVFc) poly(3-ferrocenylpropyl methacrylamide) (PFPMAm) is evaluated. PVFc has a higher Re/Mo separation factor compared to PFPMAm 0.6 V Ag/AgCl. In techniques show that both swell the presence (having solvation PFPMAm), but do not contact MoO42–. Ab simulations suggest maintains well-defined double shell ReO4–. more loosely solvated anion (ReO4–) preferably adsorbed by hydrophobic redox polymer (PVFc), electrostatic cross-linking driven divalent anionic interactions could impair film swelling. Thus, in-depth understanding mechanisms can accelerate design ion-selective redox-mediated systems transition recovery recycling.

Language: Английский

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Olefin-Assisted Electrochemical Recycling of Homogeneous Hydrosilylation Catalysts in Nonpolar Media

JACS Au, Journal Year: 2025, Volume and Issue: 5(3), P. 1221 - 1231

Published: Feb. 27, 2025

Homogeneous platinum catalysts for hydrosilylation are essential the chemical industry and society, through production of commodities such as functional silicones. However, high boiling points products low concentration homogeneous make implementation traditional separation methods difficult. Catalyst loss becomes a core sustainability techno-economic challenge. In addition, highly active platinum-based have remarkable susceptibility to deactivation upon reaction completion. Recently, redox-mediated electrosorption has been successfully demonstrated in number electrically conductive media platform. industrial systems carried out nonconductive media. Therefore, developing an electrochemical recycling system realistic, can be transformative sustainable catalysis manufacturing. Here, we overcome these challenges catalyst by introducing strongly coordinating vinyl ligand enabling Pt solvent-free, nonpolar reactant two distinct loops electrosorbent regeneration. The olefin maintains catalytic activity after prevents particle aggregation, primary mechanism deactivation. stabilized coordinated reversibly adsorbed released electrosorbent, demonstrating 100% retention over 90% release efficiency. A analysis supports economic potential system, with cost savings >5k USD/kgPt. By combining design engineering, demonstrate industrially relevant practical

Language: Английский

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Multi-Ferrocene-Based Ligands: From Design to Applications

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Despite the extensive literature on ferrocene chemistry, a comprehensive analysis of multiferrocene ligands is notably absent. Thus, this review presents an overview multiferrocenyl-containing ligands, focusing their synthesis, characterization, and applications in catalysis sensing. These offer unique properties, including redox activity planar chirality, making them valuable asymmetric molecular electronics. The covers from first synthesis tris(ferrocenyl)phosphane 1962 to current developments, various ligand subsets, which contain at least two units within structure. Special attention given explaining coordination electrochemical behavior, practical these ligands. aim undertaking fill gaps knowledge inspire further research by identifying areas for exploration. Notably, certain families like TRAP (trans-spanning phosphane) remain underexplored terms highlighting opportunities future investigation. provides resource researchers field, stimulating advancements multiferrocenyl chemistry its wide-ranging applications.

Language: Английский

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Selective electrochemical recovery of cerium over lanthanum from complex waste feedstocks by alternating current electro-precipitation

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 504, P. 158537 - 158537

Published: Dec. 11, 2024

Language: Английский

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