Robust Electrocatalytic CO2 Reduction in Acid Enabled by "Molecularly Charged" Cobalt Phthalocyanine: A Profound Understanding from Electric Double Layer.

Electrocatalytic CO2 reduction (eCO2R) in acid holds promise in renewable electricity-powered CO2 utilization with high efficiency, but the hydrogen evolution reaction (HER) often prevails and results in a low eCO2R selectivity. Here, using cobalt phthalocyanine/Ketjen black (CoPc/KB) as the model catalysts, we systematically study the effect of active site density, operational current density, and hydrated cations on the acidic eCO2R selectivity and decipher it through the componential dynamics of electric double layer (EDL). The optimal CoPc-4/KB demonstrates a near-unity CO Faradaic efficiency from 50 to 400 mA cm-2 and superb operational stability (>120 h) at 100 mA cm-2. Aided by in situ Raman and infrared spectroscopies, we reveal that the proper cations establish an electrostatic shield for mitigating bulk H+ penetration and mediate the interfacial water structure for suppressing HER. This study should elicit further profound thinking on robust eCO2R system design from the perspective of multiphasic and dynamic EDL.

Manipulating Hierarchical Orientation of Wet-Spun Hybrid Fibers via Rheological Engineering for Zn-Ion Fiber Batteries.

Wet-spinning is a promising strategy to fabricate fiber electrodes for real commercial fiber battery applications, according to its great compatibility with large-scale fiber production. However, engineering the rheological properties of the electrochemical active materials to accommodate the viscoelasticity or liquid crystalline requirements for continuous wet-spinning remains a daunting challenge. Here, with entropy-driven volume-exclusion effects, the rheological behavior of vanadium pentoxide (V2 O5 ) nanowire dispersions is regulated through introducing 2D graphene oxide (GO) flakes in an optimal ratio. By optimizing the viscoelasticity and liquid-crystalline behavior of the spinning dope, the wet-spun hybrid fibers display controlled hierarchical orientation. The wet-spun V2 O5 /rGO hybrid fiber with the optimal 10:1 mass fraction (V2 O5 /rGO10:1 ) exhibits a highly oriented nanoblock arrangement, enabling efficient Zn-ion migration and an excellent Zn-ion storage capacity of 486.03 mAh g-1 at 0.1 A g-1 . A half-meter long quasi-solid-state fiber Zn-ion battery is assembled with a polyacrylamide gel electrolyte and biocompatible Ecoflex encapsulation. The thus-derived fiber Zn-ion battery is integrated into a wearable self-powered system, incorporating a highly efficient GaAs solar cell, which delivers a record-high overall efficiency (9.80%) for flexible solar charging systems.