A Cross-linked n-Type Conjugated Polymer with Polar Side Chains Enables Ultrafast Pseudocapacitive Energy Storage.

Pseudocapacitors bridge the performance gap between batteries and electric double-layer capacitors by storing energy via a combination of fast surface/near-surface Faradaic redox processes and electrical double-layer capacitance. Organic semiconductors are an emerging class of pseudocapacitive materials that benefit from facile synthetic tunability and mixed ionic-electronic conduction. Reported examples are mostly limited to p-type (electron-donating) conjugated polymers, while n-type (electron-accepting) examples remain comparatively underexplored. This work introduces a new cross-linked n-type conjugated polymer, spiro-NDI-N, strategically designed with polar tertiary amine side chains. This molecular design aims to synergistically increase the electroactive surface area and boost ion transport for efficient ionic-electronic coupling. Spiro-NDI-N demonstrates excellent pseudocapacitive energy storage performance in pH-neutral aqueous electrolytes, with specific capacitance values of up to 532 F g-1 at 5 A g-1 and stable cycling over 5000 cycles. Moreover, it maintains a rate capability of 307 F g-1 at 350 A g-1. The superior pseudocapacitive performance of spiro-NDI-N, compared to strategically designed structural analogues lacking either the cross-linked backbone or polar side chains, validates the essential role of its molecular design elements. More broadly, the design and performance of spiro-NDI-N provide a novel strategy for developing high-performance organic pseudocapacitors.

Conjugated Polyelectrolyte Thin Films for Pseudocapacitive Applications.

A subclass of organic semiconductors known as conjugated polyelectrolytes (CPEs) is characterized by a conjugated backbone with ionic pendant groups. The water solubility of CPEs typically hinders applications of thin films in aqueous media. Herein, it is reported that films of an anionic CPE, namely CPE-K, drop cast from water produces single-component solid-state pseudocapacitive electrodes that are insoluble in aqueous electrolyte. That X-ray diffraction experiments reveal a more structurally ordered film, relative to the as-obtained powder from chemical synthesis, and dynamic light scattering measurements show an increase in aggregate particle size with increasing [KCl] indicate that CPE-K films are insoluble because of tight interchain contacts and electrostatic screening by the electrolyte. CPE-K film electrodes can maintain 85% of their original capacitance (84 F g-1 ) at 500 A g-1 and exhibit excellent cycling stability, where a capacitance retention of 93% after 100 000 cycles at a current density of 35 A g-1 . These findings demonstrate that it is possible to use initially water soluble ionic-organic materials in aqueous electrolytes, by increasing the electrolyte concentration. This strategy can be applied to the application of conjugated polyelectrolytes in batteries, organic electrochemical transistors, and electrochemical sensors, where fast electron and ion transport are required.

Recyclable Conjugated Polyelectrolyte Hydrogels for Pseudocapacitor Fabrication.

In alignment with widespread interest in carbon neutralization and sustainable practices, we disclose that conjugated polyelectrolyte (CPE) hydrogels are a type of recyclable, electrochemically stable, and environmentally friendly pseudocapacitive material for energy storage applications. By leveraging ionic-electronic coupling in a relatively fluid medium, one finds that hydrogels prepared using a fresh batch of an anionic CPE, namely, Pris-CPE-K, exhibit a specific capacitance of 32.6 ± 6.6 F g-1 in 2 M NaCl and are capable of 80% (26.1 ± 6.5 F g-1) capacitance retention after 100,000 galvanostatic charge-discharge (GCD) cycles at a current density (J) of 10 A g-1. We note that equilibration under a constant potential prior to GCD analysis leads to the K+ counterions in the CPE exchanging with Na+ and, thus, the relevant active material Pris-CPE-Na. It is possible to remove the CPE material from the electrochemical cell via extraction with water and to carry out a simple purification through dialysis to produce a recycled material, namely Re-CPE-Na. The recycling workup has no significant detrimental impact on the electrochemical performance. Specifically, Re-CPE-Na hydrogels display an initial specific capacitance of 26.3 ± 1.2 F g-1 (at 10 A g-1) and retain 77% of the capacitance after a subsequent 100,000 GCD cycles. Characterization by NMR, FTIR, and Raman spectroscopies, together with XPS and GPC measurements, revealed no change in the structure of the backbone or side chains. However, rheological measurements gave evidence of a slight loss in G' and G''. Overall, that CPE hydrogels display recyclability argues in favor of considering them as a novel materials platform for energy storage applications within an economically viable circular recycling strategy.

A Broad Light-Harvesting Conjugated Oligoelectrolyte Enables Photocatalytic Nitrogen Fixation in a Bacterial Biohybrid.

We report a rationally designed membrane-intercalating conjugated oligoelectrolyte (COE), namely COE-IC, which endows aerobic N2 -fixing bacteria Azotobacter vinelandii with a light-harvesting ability that enables photosynthetic ammonia production. COE-IC possesses an acceptor-donor-acceptor (A-D-A) type conjugated core, which promotes visible light absorption with a high molar extinction coefficient. Furthermore, COE-IC spontaneously associates with A. vinelandii to form a biohybrid in which the COE is intercalated within the lipid bilayer membrane. In the presence of L-ascorbate as a sacrificial electron donor, the resulting COE-IC/A. vinelandii biohybrid showed a 2.4-fold increase in light-driven ammonia production, as compared to the control. Photoinduced enhancement of bacterial biomass and production of L-amino acids is also observed. Introduction of isotopically enriched 15 N2 atmosphere led to the enrichment of 15 N-containing intracellular metabolites, consistent with the products being generated from atmospheric N2 .

An n-Type Conjugated Oligoelectrolyte Mimics Transmembrane Electron Transport Proteins for Enhanced Microbial Electrosynthesis.

Interfacing bacteria as biocatalysts with an electrode provides the basis for emerging bioelectrochemical systems that enable sustainable energy interconversion between electrical and chemical energy. Electron transfer rates at the abiotic-biotic interface are, however, often limited by poor electrical contacts and the intrinsically insulating cell membranes. Herein, we report the first example of an n-type redox-active conjugated oligoelectrolyte, namely COE-NDI, which spontaneously intercalates into cell membranes and mimics the function of endogenous transmembrane electron transport proteins. The incorporation of COE-NDI into Shewanella oneidensis MR-1 cells amplifies current uptake from the electrode by 4-fold, resulting in the enhanced bio-electroreduction of fumarate to succinate. Moreover, COE-NDI can serve as a "protein prosthetic" to rescue current uptake in non-electrogenic knockout mutants.

Enabling Electron Injection for Microbial Electrosynthesis with n-Type Conjugated Polyelectrolytes.

Microbial electrosynthesis-using renewable electricity to stimulate microbial metabolism-holds the promise of sustainable chemical production. A key limitation hindering performance is slow electron-transfer rates at biotic-abiotic interfaces. Here a new n-type conjugated polyelectrolyte is rationally designed and synthesized and its use is demonstrated as a soft conductive material to encapsulate electroactive bacteria Shewanella oneidensis MR-1. The self-assembled 3D living biocomposite amplifies current uptake from the electrode ≈674-fold over controls with the same initial number of cells, thereby enabling continuous synthesis of succinate from fumarate. Such functionality is a result of the increased number of bacterial cells having intimate electronic communication with the electrode and a higher current uptake per cell. This is underpinned by the molecular design of the polymer to have an n-dopable conjugated backbone for facile reduction by the electrode and zwitterionic side chains for compatibility with aqueous media. Moreover, direct arylation polycondensation is employed instead of the traditional Stille polymerization to avoid non-biocompatible tin by-products. By demonstrating synergy between living cells with n-type organic semiconductor materials, these results provide new strategies for improving the performance of bioelectrosynthesis technologies.

Conjugated Polyelectrolyte/Bacteria Living Composites in Carbon Paper for Biocurrent Generation.

Successful practical implementation of bioelectrochemical systems (BES) requires developing affordable electrode structures that promote efficient electrical communication with microbes. Recent efforts have centered on immobilizing bacteria with organic semiconducting polymers on electrodes via electrochemical methods. This approach creates a fixed biocomposite that takes advantage of the increased electrode's electroactive surface area (EASA). Here, it is demonstrated that a biocomposite comprising the water-soluble conjugated polyelectrolyte CPE-K and electrogenic Shewanella oneidensis MR-1 can self-assemble with carbon paper electrodes, thereby increasing its biocurrent extraction by ≈6-fold over control biofilms. A ≈1.5-fold increment in biocurrent extraction is obtained for the biocomposite on carbon paper relative to the biocurrent extracted from gold-coated counterparts. Electrochemical characterization revealed that the biocomposite stabilized with the carbon paper more quickly than atop flat gold electrodes. Cross-sectional images show that the biocomposite infiltrates inhomogeneously into the porous carbon structure. Despite an incomplete penetration, the biocomposite can take advantage of the large EASA of the electrode via long-range electron transport. These results show that previous success on gold electrode platforms can be improved when using more commercially viable and easily manipulated electrode materials.

Conjugated Polyelectrolytes: Underexplored Materials for Pseudocapacitive Energy Storage.

Conjugated polyelectrolytes (CPEs) are characterized by an electronically delocalized backbone bearing ionic functionalities. These features lead to properties relevant for use in energy-storing pseudocapacitor devices, including ionic conductivity, water processability, gel-formation, and formation of polaronic species stabilized by electrostatic interactions. In this Perspective, the basis for evaluating the figures of merit for pseudocapacitors is provided, together with the techniques used for their evaluation. The general utility and challenges encountered with neutral conjugated polymers are then discussed. Finally, recent advances on the use of CPEs in pseudocapacitor devices are reviewed. The article is concluded by discussing how their miscibility in aqueous media permits the incorporation of CPEs in living materials that are capable of switching function from extraction of energy from bacterial metabolic pathways to pseudocapacitor energy storage.

Phosphine-Catalyzed (3+2) Annulation of Isoindigos with Allenes: Enantioselective Formation of Two Vicinal Quaternary Stereogenic Centers.

Construction of contiguous all-carbon quaternary stereogenic centers is a long-standing challenge in synthetic organic chemistry. In this report, a phosphine-catalyzed enantioselective (3+2) annulation reaction between allenes and isoindigos, containing either two identical or different oxindole moieties, is introduced as a powerful strategy for the construction of spirocyclic bisindoline alkaloid core structures. The reported reactions feature high chemical yields, excellent enantioselectivities, and very good regioselectivities, and are highly useful for creating structurally challenging bisindoline natural products.