Redox-Responsive Halogen Bonding as a Highly Selective Interaction for Electrochemical Separations.

Leveraging specific noncovalent interactions can broaden the mechanims for selective electrochemical separations beyond solely electrostatic interactions. Here, we explore redox-responsive halogen bonding (XB) for selective electrosorption in nonaqueous media, by taking advantage of directional interactions of XB alongisde a cooperative and synergistic ferrocene redox-center. We designed and evaluated a new redox-active XB donor polymer, poly(5-iodo-4-ferrocenyl-1-(4-vinylbenzyl)-1H-1,2,3-triazole) (P(FcTS-I)), for the electrochemically switchable binding and release of target organic and inorganic ions at a heterogeneous interface. Under applied potential, the oxidized ferrocene amplifies the halogen binding site, leading to significantly enhanced uptake and selectivity towards key inorganic and organic species, including chloride, bisulfate, and benzenesulfonate, compared to the open-circuit potential or the hydrogen bonding donor analog. Density functional theory calculations, as well as spectroscopic analysis, offer mechanistic insight into the degree of amplification of σ-holes at a molecular level, with selectivity modulated by charge transfer and dispersion interactions. Our work highlights the potential of XB in selective electrosorption by uniquely leveraging noncovalent interactions for redox-mediated electrochemical separations.

Redox-Functionalized Semiconductor Interfaces for Photoelectrochemical Separations.

Redox-mediated electrosorption is a promising platform for selective electrochemical (EC) separations, due to its molecular selectivity, high uptake, and tunability for target ions. However, the electrical energy required is mainly generated by non-renewable energy sources, which limits its sustainability and overall impact to decarbonization. Here, a redox-mediated photoelectrochemical (PEC) separation process using polyvinyl ferrocene functionalized TiO2 nanorod electrodes is proposed, which integrates direct solar energy as a driver for the selective electrosorption. The photoelectrochemically-driven oxidation and reduction with both homogeneous and heterogeneous ferrocene-systems is investigated to establish the underlying mechanism. The PEC system can separate heavy metal oxyanions at lower voltages or even without electrical energy. At 0.3 V versus SCE, a 124 mg g-1 uptake for Mo is achieved, which is comparable to the performance of EC cells at 0.75 V versus SCE. Thus, PEC systems not only can generate energy for spontaneous redox-separations, but also can reduce electrical energy consumption by 51.4% compared to EC cells for separation processes when coupled with an external electrical energy.

Investigating the Electrochemically Driven Capture and Release of Long-Chain PFAS by Redox Metallopolymer Sorbents.

The remediation of perfluoroalkyl substances (PFAS) is an urgent challenge due to their prevalence and persistence in the environment. Electrosorption is a promising approach for wastewater treatment and water purification, especially through the use of redox polymers to control the binding and release of target contaminants without additional external chemical inputs. However, the design of efficient redox electrosorbents for PFAS faces the significant challenge of balancing a high adsorption capacity while maintaining significant electrochemical regeneration. To overcome this challenge, we investigate redox-active metallopolymers as a versatile synthetic platform to enhance both electrochemical reversibility and electrosorption uptake capacity for PFAS removal. We selected and synthesized a series of metallopolymers bearing ferrocene and cobaltocenium units spanning a range of redox potentials to evaluate their performance for the capture and release of perfluorooctanoic acid (PFOA). Our results demonstrate that PFOA uptake and regeneration efficiency increased with more negative formal potential of the redox polymers, indicating possible structural correlations with the electron density of the metallocenes. Poly(2-(methacryloyloxy)ethyl cobaltoceniumcarboxylate hexafluorophosphate) (PMAECoPF6) showed the highest affinity toward PFOA, with an uptake capacity of more than 90 mg PFOA/g adsorbent at 0.0 V vs Ag/AgCl and a regeneration efficiency of more than 85% at -0.4 V vs Ag/AgCl. Kinetics of PFOA release showed that electrochemical bias greatly enhanced the regeneration efficiency when compared to open-circuit desorption. In addition, electrosorption of PFAS from different wastewater matrices and a range of salt concentrations demonstrated the capability of PFAS remediation in complex water sources, even at ppb levels of contaminants. Our work showcases the synthetic tunability of redox metallopolymers for enhanced electrosorption capacity and regeneration of PFAS.

Imparting Selective Fluorophilic Interactions in Redox Copolymers for the Electrochemically Mediated Capture of Short-Chain Perfluoroalkyl Substances.

With increasing regulations on per- and polyfluoroalkyl substances (PFAS) across the world, understanding the molecular level interactions that drive their binding by functional adsorbent materials is key to effective PFAS removal from water streams. With the phaseout of legacy long-chain PFAS, the emergence of short-chain PFAS has posed a significant challenge for material design due to their higher mobility and hydrophilicity and inefficient removal by conventional treatment methods. Here, we demonstrate how cooperative molecular interactions are essential to target short-chain PFAS (from C4 to C7) by tailoring structural units to enhance affinity while modulating the electrochemical control of capture and release of PFAS. We report a new class of fluorinated redox-active amine-functionalized copolymers to leverage both fluorophilic and electrostatic interactions for short-chain PFAS binding. We combine molecular dynamics (MD) simulations and electrosorption to elucidate the role of the designer functional groups in enabling affinity toward short-chain PFAS. Preferential interaction coefficients from MD simulations correlated closely with experimental trends: fluorination enhanced the overall PFAS uptake and promoted the capture of less hydrophobic short-chain PFAS (C ≤ 5), while electrostatic interactions provided by secondary amine groups were sufficient to capture PFAS with higher hydrophobicity (C ≥ 6). The addition of an induced electric field showed favorable kinetic enhancement for the shortest PFAS and increased the reversibility of release from the electrode. Integration of these copolymers with electrochemical separations showed potential for removing these contaminants at environmentally relevant conditions while eliminating the need for chemical regeneration.

Electrochemical recycling of homogeneous catalysts.

Homogeneous catalysts have rapid kinetics and keen reaction selectivity. However, their widespread use for industrial catalysis has remained limited because of challenges in reusability. Here, we propose a redox-mediated electrochemical approach for catalyst recycling using metallopolymer-functionalized electrodes for binding and release. The redox platform was investigated for the separation of key platinum and palladium homogeneous catalysts used in organic synthesis and industrial chemical manufacturing. Noble metal catalysts for hydrosilylation, silane etherification, Suzuki cross-coupling, and Wacker oxidation were recycled electrochemically. The redox electrodes demonstrated high sorption uptake for platinum-based catalysts (Qmax up to 200 milligrams of platinum per gram of adsorbent) from product mixtures, with up to 99.5% recovery, while retaining full catalytic activity over multiple cycles. The combination of mechanistic studies and electronic structure calculations indicate that selective interactions with anionic intermediates during the catalytic cycle played a key role in the separations. Last, continuous flow cell studies support the scalability and favorable technoeconomics of electrochemical recycling.

Asymmetric Redox-Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic.

Advanced redox-polymer materials offer a powerful platform for integrating electroseparations and electrocatalysis, especially for water purification and environmental remediation applications. The selective capture and remediation of trivalent arsenic (As(III)) is a central challenge for water purification due to its high toxicity and difficulty to remove at ultra-dilute concentrations. Current methods present low ion selectivity, and require multistep processes to transform arsenic to the less harmful As(V) state. The tandem selective capture and conversion of As(III) to As(V) is achieved using an asymmetric design of two redox-active polymers, poly(vinyl)ferrocene (PVF) and poly-TEMPO-methacrylate (PTMA). During capture, PVF selectively removes As(III) with exceptional uptake (>100 mg As/g adsorbent), and during release, synergistic electrocatalytic oxidation of As(III) to As(V) with >90% efficiency can be achieved by PTMA, a radical-based redox polymer. The system demonstrates >90% removal efficiencies with real wastewater and concentrations of arsenic as low as 10 ppb. By integrating electron-transfer through the judicious design of asymmetric redox-materials, an order-of-magnitude energy efficiency increase can be achieved compared to non-faradaic, carbon-based materials. The study demonstrates for the first time the effectiveness of asymmetric redox-active polymers for integrated reactive separations and electrochemically mediated process intensification for environmental remediation.

Molecular ring rotation in poly(vinylferrocene).

We investigate the ring rotation dynamics in poly(vinylferrocene) (PVFc) using incoherent neutron spectroscopy. PVFc contains ferrocene units laterally attached to a polymer backbone, allowing for one cyclopentadienyl ring of the organometallic sandwich structure of ferrocene to undergo rotational jump diffusion. The barrier of rotation is found to be broadly distributed, but the dynamics can be well described using a rotation rate distribution model which is well known from the description of methyl group rotation in glassy polymers. As necessary information for the analysis of quasielastic scattering data, we measure the static structure factor of the polymer using polarized neutron diffraction. Neutron time-of-flight and backscattering data are then combined and consistently modeled over the large temperature range from 80 K to 350 K yielding an Arrhenius behavior of the jump rate distribution. The mean value of potential barrier distribution is found to be 〈EA〉 = 9.61(2) kJ mol-1 with a root mean square width of σE = 3.12(1) kJ mol-1, being the result of superposition of constant intramolecular and heterogeneous intermolecular rotational barriers.

Metallopolymer-Based Shape Anisotropic Nanoparticles.

The formation of nanostructured shape anisotropic nanoparticles from poly(ferrocenylsilane)-b-poly(2-vinylpyridine) (PFS-b-P2VP) block copolymers is presented. Ellipsoidal particles with an axially stacked lamellar structure and nanosheets with a hexagonal structure of PFS cylinders are obtained under neutral wetting conditions through the use of a mixed surfactant system during self-assembly. In contrast to traditional systems, the resulting particle structure is strongly influenced by crystallization of the PFS domains under colloidal confinement with lamella-forming PFS-b-P2VP block copolymers leading to cylindrical morphologies. A blending approach was developed to control this morphological change and by the addition of PFS homopolymers, ellipsoidal particles with a lamellar structure could also be obtained. Ultimately, the spatial control over two orthogonal functionalities was exploited to demonstrate morphology transitions for nanosheets upon the exposure to methanol as solvent for P2VP and FeCl3 as a redox stimulus, opening up a variety of applications in the field of stimuli-responsive materials.

Surface-initiated anionic polymerization of [1]silaferrocenophanes for the preparation of colloidal preceramic materials.

A novel strategy for the preparation of poly(ferrocenylsilane) (PFS) immobilized on the surface of cross-linked polystyrene (PS) nanoparticles is reported. The ferrocene-containing core/shell architectures are shown to be excellent candidates as preceramic polymers yielding spherical ceramic materials consisting of iron silicide (Fe3 Si) and metallic iron after thermal treatment. For this purpose, dimethyl- and hydromethyl[1]silaferrocenophane monomers are polymerized by surface-initiated ring-opening polymerization upon taking advantage of residual vinylic moieties at the PS particle surface. A strategy for selective chain growth from the particle surface is developed without the formation of free PFS homopolymer in solution. The grafted particles are characterized using transmission electron microscopy (TEM) and dynamic light scattering (DLS). These particles are excellent precursors for ceramics as studied by thermogravimetric analysis (TGA). The composition of the ceramics is studied using X-ray diffraction (XRD) measurements, while the morphology is probed by scanning electron microscopy (SEM) revealing the original spherical shape of the precursor particles. Obtained ceramic materials- predominantly based on iron silicides-show ferromagnetic behavior as investigated by superconducting quantum interference device (SQUID) magnetization measurements at different temperatures.

Individually addressable thermo- and redox-responsive block copolymers by combining anionic polymerization and RAFT protocols.

A novel diblock copolymer consisting of poly(vinylferrocene) (PVFc) and poly(N,N-diethylacrylamide) (PDEA) is synthesized via a combination of anionic and RAFT polymerization. The use of a novel route to hydroxyl-end-functionalized metallopolymers in anionic polymerization and subsequent esterification with a RAFT agent leads to a PVFc macro-CTA (M¯n = 3800 g mol(-1) ; D = 1.17). RAFT polymerization with DEA affords block copolymers as evidenced by (1) H NMR spectroscopy as well as size exclusion chromatography (6400 ≤ M¯n≤ 33700 g mol(-1) ; 1.31 ≤ D 1.28). Self-assembly of the amphiphilic block copolymers in aqueous solution leads to micelles as shown via TEM. Importantly, the distinct thermo-responsive and redox-responsive character of the blocks is probed via dynamic light scattering and found to be individually and repeatedly addressable.

Responsive vesicles from the self-assembly of crystalline-coil polyferrocenylsilane-block-poly(ethylene oxide) star-block copolymers.

We demonstrate the synthesis and characterization of star-shaped crystalline-coil block copolymers with four arms consisting of an inner block of poly(ethylene oxide) and an outer semicrystalline compartment of poly(ferrocenyldimethylsilane), [PEO(50) -b-PFDMS(35)](4). The materials were synthesized by transition-metal-catalyzed ring-opening polymerization of dimethylsila[1]ferrocenophane in the presence of silane-functionalized four-arm PEO stars as macroinitiators and they exhibited a moderate polydispersity (PDI≅1.4). Self-assembly in mixtures of THF and different alcohols as selective solvents for the PEO block resulted in the formation of semicrystalline vesicles (ethanol, 1-butanol) or large, rather ill-defined, spherical structures (methanol). Further, both the rate of addition of the selective co-solvent and the overall solvent/non-solvent ratio drastically affected the size and stability of the self-assembled particles. We could also show that a photoacid generator, as a model for an active substance, can be encapsulated and the UV-induced generation of HCl resulted in a straightforward degradation of the organometallic vesicles.