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.

Emerging as a new frontier in heterogeneous catalysis, single-atom site catalysts (SSCs) have sparked enormous attention and bring about new opportunities to oxygen reduction electrocatalysis. Despite considerable progress achieved recently, most of the reported SSCs suffer from either insufficient activity or unsatisfactory stability, which severely retards their practical application. Here, we demonstrate a novel Ru-SSC with appropriate adsorption free energy of OH* (ΔG OH*) to confer excellent activity and low Fenton reactivity to maintain long-term stability. The as-developed Ru-SSC exhibits encouraging oxygen reduction reaction turnover frequency of 4.99 e– s–1 sites–1, far exceeding the state-of-the-art Fe-SSC counterpart (0.816 e– s–1 sites–1), as a result of Ru energy level regulation via spontaneous OH binding. Furthermore, Ru-SSC exhibits greatly suppressed Fenton reactivity, with restrained generation of reactive oxygen species directly observed, thus endowing the Ru-SSC with much more superior stability (only 17 mV negative shift after 20 000 cycles) than the Fe-SSC counterpart (31 mV). The practical application of Ru-SSC is further validated by its excellent activity and stability in a real fuel cell device.

Development of inexpensive and efficient oxygen evolution reaction (OER)catalysts in acidic environment is very challenging, but important for practical proton exchange membrane (PEM) water electrolyzers. Here we develop a molecular iron-nitrogen coordinated carbon nanofiber supported on electrochemically exfoliated graphene (FeN 4 /NF/EG) electrocatalyst through carbonizing the precursor composed of iron ions absorbed on polyaniline-electrodeposited EG. Benefitting from the unique 3D structure, the FeN 4 /NF/EG hybrid exhibits a low overpotential of ~294 mV at 10 mA cm -2 for the OER in This article is protected by copyright. All rights reserved. 5precursor was uniformly electrodeposited on EG surface that was constructed by electrochemical exfoliation of graphite (Figure S1). After soaking in iron nitrate solution, carbonization, and acid etching treatments, the precursor was in situ converted into FeN x /NF/EG catalyst, which is supported by Fourier-transform infrared spectroscopy (FTIR) results (Figure S2). We systematically explored the influence of annealing at different temperatures (800-1000 o C) affecting the OER activity. The optimized carbonization temperature was 900 o C (FeN x /NF/EG), which exhibited the best electrocatalytic performance for OER in acid (Figure S3-S4). Moreover, this synthesis method can be further This article is protected by copyright. All rights reserved. 13 support from U.S. DOE fuel cell technologies Offices. M. Qiu thanks the support of Self-determined Research Funds of CCNU from Colleges' Basic Research and Operation of MOE ( 23020205170456). This research was supported by Dr. Y. Hu (Yongfeng Hu) to provide valuable discussion about the XAS analysis.Received: ((will be filled by the editorial staff))Revised: ((will be filled by the editorial staff))

The intrinsically sluggish kinetics of oxygen reduction reaction (ORR) and overuse of expensive and unstable Pt-based catalysts have severely hampered the development of clean energy technologies. Herein, a type of...