Atomically-precise preparation and atomic-level understanding on the single-atomic active sites with unique coordination structures in electrocatalysts for CO2 reduction reaction (CO2RR) remain a challenge. Here, we report a strategy of...

Oxygen reduction reaction (ORR) is an important half reaction in fuel cells and metal–air batteries as well as in cost-effective electrosynthesis of H2O2. However, the issues of low selectivity and...

Cu single-atom catalysts (Cu SACs) have been considered as promising catalysts for efficient electrocatalytic CO 2 reduction reactions (ECRRs). However, the reports on Cu SACs with an asymmetric atomic interface to obtain CO are few. Herein, we rationally designed two Cu SACs with different asymmetric atomic interfaces to explore their catalytic performance. The catalyst of CuN 3 O/C delivers high ECRR selectivity with an FE CO value of above 90% in a wide potential window from −0.5 to −0.9 V vs RHE (in particular, 96% at −0.8 V), while CuCO 3 /C delivers poor selectivity for CO production with a maximum FE CO value of only 20.0% at −0.5 V vs RHE. Besides, CuN 3 O/C exhibited a large turnover frequency (TOF) up to 2782.6 h −1 at −0.9 V vs RHE, which is much better than the maximum 4.8 h −1 of CuCO 3 /C. Density functional theory (DFT) results demonstrate that the CuN 3 O site needs a lower Gibbs free energy than CuCO 3 in the rate-determining step of CO desorption, leading to the outstanding performance of CuN 3 O/C on the process of ECRR-to-CO. This work provides an efficient strategy to improve the selectivity and activity of the ECRR via regulating asymmetric atomic interfaces of SACs by adjusting the coordination atoms.

Constructing electrocatalysts with p‐block elements is generally considered rather challenging owing to their closed d shells. Here for the first time, we present a p‐block‐element bismuth‐based (Bi‐based) catalyst with the co‐existence of single‐atomic Bi sites coordinated with oxygen (O) and sulfur (S) atoms and Bi nanoclusters (Biclu) (collectively denoted as BiOSSA/Biclu) for the highly selective oxygen reduction reaction (ORR) into hydrogen peroxide (H2O2). As a result, BiOSSA/Biclu gives a high H2O2 selectivity of 95 % in rotating ring‐disk electrode, and a large current density of 36 mA cm−2 at 0.15 V vs. RHE, a considerable H2O2 yield of 11.5 mg cm−2 h−1 with high H2O2 Faraday efficiency of ∼90 % at 0.3 V vs. RHE and a long‐term durability of ∼22 h in H‐cell test. Interestingly, the experimental data on site poisoning and theoretical calculations both revealed that, for BiOSSA/Biclu, the catalytic active sites are on the Bi clusters, which are further activated by the atomically dispersed Bi coordinated with O and S atoms. This work demonstrates a new synergistic tandem strategy for advanced p‐block‐element Bi catalysts featuring atomic‐level catalytic sites, and the great potential of rational material design for constructing highly active electrocatalysts based on p‐block metals.

For metal–carbon shell catalysts of hydrogen evolution reaction (HER), owing to the diversity of the inner metal phases and the adjustability of outer carbon structure, the structure of the active...