Mao, Haiyan | Search NASA

DOE OSTI2025

Manipulating Aromaticity to Redirect Topochemical Polymerization Pathways

Topochemical polymerization (TCP) represents an essential route to create regio- and stereoregular polymers through solid-state transformations. Herein, we present an innovative strategy for controlling topochemical polymerization pathways by tailoring the terminal group aromaticity in the para-azaquinodimethane (AQM) ring system. Substituting phenyl groups with less aromatic furyl units extends significant spin density delocalization across the conjugated core upon thermal activation, inducing significant diradicaloid characters at furyl positions and enabling unconventional reactivities in both solution and solid states. Thermal treatment in toluene yields a unique cyclophane dimer formed via furyl-methine C-C coupling, confirmed by X-ray crystallography, while solid-state reactions produce polymers formed via both intercolumnar furyl-methine coupling and intracolumnar methine-methine coupling. The spin-center-directed mechanism underlying these transformations is validated through theoretical modeling and isotopic labeling experiments. This study highlights the prowess of aromaticity modulation in functional pro-aromatic systems, which enables the synthesis of polymers with main chain structures that are otherwise difficult to access.

Zhang, Qingsong↗

DOE OSTI2024

Dynamic Bubbling Balanced Proactive CO 2 Capture and Reduction on a Triple-Phase Interface Nanoporous Electrocatalyst

The formation and preservation of the active phase of the catalysts at the triple-phase interface during CO 2 capture and reduction is essential for improving the conversion efficiency of CO 2 electroreduction toward value-added chemicals and fuels under operational conditions. Designing such ideal catalysts that can mitigate parasitic hydrogen generation and prevent active phase degradation during the CO 2 reduction reaction (CO 2 RR), however, remains a significant challenge. Herein, we developed an interfacial engineering strategy to build a new SnO x catalyst by invoking multiscale approaches. This catalyst features a hierarchically nanoporous structure coated with an organic F-monolayer that modifies the triple-phase interface in aqueous electrolytes, substantially reducing competing hydrogen generation (less than 5%) and enhancing CO 2 RR selectivity (~90%). This rationally designed triple-phase interface overcomes the issue of limited CO 2 solubility in aqueous electrolytes via proactive CO 2 capture and reduction. Concurrently, we utilized pulsed square-wave potentials to dynamically recover the active phase for the CO 2 RR to regulate the production of C1 products such as formate and carbon monoxide (CO). This protocol ensures profoundly enhanced CO 2 RR selectivity (~90%) compared with constant potential (~70%) applied at -0.8 V (V vs RHE). We further achieved a mechanistic understanding of the CO 2 capture and reduction processes under pulsed square-wave potentials via in situ Raman spectroscopy, thereby observing the potential-dependent intensity of Raman vibrational modes of the active phase and CO 2 RR intermediates. Finally, this work will inspire material design strategies by leveraging triple-phase interface engineering for emerging electrochemical processes, as technology moves toward electrification and decarbonization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗