Efforts in a large number of transition metal-carbon systems are devoted to the development of efficient catalysts for oxygen reduction reaction (ORR). However, unsatisfied O₂ adsorption and slow reduction of OH* at the active centers hinder the further development of these catalysts. We here report a gasifiable reductant strategy, of which a new Cu-based metal organic framework (MOF: termed NTU-83) nanosheet was co-pyrolyzed with melamine to produce the N-coordinated atomic Cu and multi-oxidated Cu₂₊₁O active centers on the carbon foam with ultrathin skeleton. The engineered electrons and configuration of the active centers boost the catalyst (Cu/NC-1000) to show superior ORR activity (E_1/2 = 0.85 V), excellent stability, and methanol resistance. Further modeling calculation and controlled experiments reveal that the Cu₂₊₁O species play a crucial role in kinetically accelerated adsorption and activation of O₂, while the N₄ coordinated atomic Cu facilitates fast reduction of OH*. Such characteristics endow the Zn-air battery that containing Cu/NC-1000 as air cathode to show a high peak power density (138 mW·cm⁻²), a high specific capacity of 763 mAh·g_Zn⁻¹, and outstanding long-term cycle stability. The plausible mechanism and excellent performance show that gasifiable reductant strategy opens up a new route for regulation of the electronic of active sites but also provides a candidate for the practical application in energy conversion/storage devices.

Safely and highly selective acetylene (C₂H₂) capture is a great challenge, because of its highly explosive nature, as well as its nearly similar molecule size and boiling point toward the main impurity of carbon dioxide (CO₂). Adsorption separation has shown a promising future. Herein, a new nanoporous coordination polymer (PCP) adsorbent with fixed and free Cu ions (termed NTU-66-Cu) was prepared through post-synthetic approach via cation exchanging from the pristine NTU-66, an anionic framework with new 3, 4, 6-c topology and two kinds of cages. The NTU-66-Cu shows significantly improved C₂H₂/CO₂ selectivity from 6 to 32 (v/v: 1/1) or 4 to 42 (v/v: 1/4) at low pressure under 298 K, along with enhanced C₂H₂ capacity (from 89.22 to 111.53 cm³·g^-1). More importantly, this observation was further validated by density functional theory (DFT) calculations and breakthrough experiments under continuous and dynamic conditions. Further, the excellent chemical stability enables this adsorbent to achieve recycle C₂H₂/CO₂ separation without loss of C₂H₂ capacity.