Electrocatalytic reduction of carbon dioxide (CO2ER) in rechargeable Zn–CO2 battery still remains a great challenge. Herein, a highly efficient CO2ER electrocatalyst composed of coordinatively unsaturated single‐atom copper coordinated with nitrogen sites anchored into graphene matrix (Cu–N2/GN) is reported. Benefitting from the unsaturated coordination environment and atomic dispersion, the ultrathin Cu–N2/GN nanosheets exhibit a high CO2ER activity and selectivity for CO production with an onset potential of −0.33 V and the maximum Faradaic efficiency of 81% at a low potential of −0.50 V, superior to the previously reported atomically dispersed Cu–N anchored on carbon materials. Experimental results manifest the highly exposed and atomically dispersed Cu–N2 active sites in graphene framework where the Cu species are coordinated by two N atoms. Theoretical calculations demonstrate that the optimized reaction free energy for Cu–N2 sites to capture CO2 promote the adsorption of CO2 molecules on Cu–N2 sites; meanwhile, the short bond lengths of Cu–N2 sites accelerate the electron transfer from Cu–N2 sites to *CO2, thus efficiently boosting the *COOH generation and CO2ER performance. A designed rechargeable Zn–CO2 battery with Cu–N2/GN nanosheets deliver a peak power density of 0.6 mW cm−2, and the charge process of battery can be driven by natural solar energy.

Electrochemical reduction of CO2 (ERC) into useful products, such as formic acid and carbon monoxide, is a fascinating approach for CO2 fixation as well as energy storage. Sn‐based materials are attractive catalysts for highly selective ERC into C1 products (including HCOOH and CO), but still suffer from high overpotential, low current density, and poor stability. Here, One‐dimensional (1D) SnO2 with wire‐in‐tube (WIT) structure is synthesized and shows superior selectivity for C1 products. Using the WIT SnO2 as the ERC catalyst, very high Faradaic efficiency of C1 products (>90%) can be achieved at a wide potential range from −0.89 to −1.29 V versus RHE, thus substantially suppressing the hydrogen evolution reaction. The electrocatalyst also exhibits excellent long‐term stability. The improved catalytic activity of the WIT SnO2 over the commercial SnO2 nanoparticle indicates that higher surface area and large number of grain boundaries can effectively enhance the ERC activity. Synthesized via a facile and low‐cost electrospinning technology, the reduced WIT SnO2 can serve as a promising electrocatalyst for efficient CO2 to C1 products conversion.

A ternary Fe2O3@Ni2P/Ni(PO3)2 hybrid with strong coupling and synergistic effects was developed for highly active OER at ultra-high current densities.