Creating and maintaining a favorable microenvironment for electrocatalytic CO₂ reduction reaction (eCO₂RR) is challenging due to the vigorous interactions with both gas and electrolyte solution during the electrocatalysis. Herein, to boost the performance of eCO₂RR, a unique synthetic method that deploys the in situ reduction of precoated precursors is developed to produce activated Ag nanoparticles (NPs) within the gas diffusion layer (GDL), where the thus-obtained Ag NPs-Skeleton can block direct contact between the active Ag sites and electrolyte. Specifically, compared to the conventional surface loading mode in the acidic media, our freestanding and binder free electrode can achieve obvious higher CO selectivity of 94%, CO production rate of 23.3 mol g⁻¹ h⁻¹, single-pass CO₂ conversion of 58.6%, and enhanced long-term stability of 8 hours. Our study shows that delivering catalysts within the GDL does not only gain the desired physical protection from GDL skeleton to achieve a superior local microenvironment for more efficient pH-universal eCO₂RR, but also manifests the pore structures to effectively address gas accumulation and flood issues.

A simple method was proposed to activate alkaline Cu(OH)₂ with an acidic ionomer, Nafion, to regulate its surface microenvironment, including hydrophobicity and local basicity. In particular, the direct complete neutralization reaction between Cu(OH)₂ and Nafion in aqueous solution induces the exposing of vast anions which can exclude the in‐situ‐formed hydroxides and raise the local basicity. Remarkably, the optimal Nafion‐activated Cu(OH)₂‐derived Cu can efficiently suppress the hydrogen evolution reaction (HER) and improve the selectivity for multi‐carbon products in the CO₂ electroreduction reaction (eCO₂RR). The H₂ Faradaic efficiency (FE) decreased to 11% at a current density of 300 mA/cm² (−0.76 V vs. RHE) in a flow cell, while the bare one with H₂ had an FE of 40%. The total eCO₂RR FE reaches as high as 83%, along with an evidently increased C₂H₄ FE of 44% as compared with the bare one (24%), and good stability (8000 s), surpassing that of most of the reported Cu(OH)₂‐derived Cu. The experimental and theoretical results both show that the strong hydrophobicity and high local basicity jointly boosted the eCO₂RR as acquired by felicitously introducing ionomer on the Cu(OH)₂‐derived Cu surface.

As a promising flexible energy source for next‐generation emerging electronic devices, the temperature adaptability and low‐temperature performance retention of flexible zinc‐air batteries (ZABs) remain a great challenge for their practical application. Herein, we report photothermal‐promoted aqueous and flexible ZABs with enhanced performance under a wide temperature range via using Ni‐doped Mn₃O₄/N‐doped reduced graphene oxide (denoted as Ni‐Mn₃O₄/N‐rGO) nanohybrids as bifunctional electrocatalysts. Upon being exposed to near‐infrared light, the Ni‐Mn₃O₄/N‐rGO exhibited a powerful photothermal effect, resulting in localized and immediate heating of the electrode. Such effects led to increased active sites, improved electrical conductivity, enhanced release of bubbles, and promoted surface reconstruction of the electrode catalyst as corroborated by simulation and operando Raman. Consequently, the catalytic performance was boosted, manifesting a superior activity indicator ΔE of 0.685 V with excellent durability. As expected, the corresponding photothermal‐assisted rechargeable ZABs possessed an excellent maximum power density (e.g., 78.76 mW cm⁻² at −10°C), superb cycling stability (e.g., over 430 cycles at −10°C), and excellent flexibility from 25°C to subzero temperature. Our work opens up new possibilities for the development of all‐climate flexible electronic devices.