The structural dynamics of the solid–liquid interfaces (SLEIs) determines the chemistry in all electrochemical processes. Here, by combining multiple operando synchrotron spectroscopies, we identify at the atomic level a general evolution of single-atom Ni at SLEIs into a near-free atom state in the electrochemical oxygen reduction reaction (ORR). We uncover that the single-atom Ni at SLEIs tends to be dynamically released from the nitrogen–carbon substrate and then forms a near-free, isolated-zigzag active site (Ni1 (2‑δ)+N2) during the reaction. This isolated-zigzag Ni1 (2‑δ)+N2 active site facilitates the adsorption and dissociation of O2 into a crucial *O intermediate within the electrical double layers, realizing a highly efficient single-atom catalyst with the best ORR performance in alkaline solutions reported thus far. These findings may pave a general way for dissecting other important structural dynamic processes at SLEIs, such as hydrogen evolution, oxygen evolution, and CO2 reduction reactions.

Uncovering the dynamics of active sites in the working conditions is crucial to realizing increased activity, enhanced stability and reduced cost of oxygen evolution reaction (OER) electrocatalysts in proton exchange membrane electrolytes. Herein, we identify at the atomic level potential-driven dynamic-coupling oxygen on atomically dispersed hetero-nitrogen-configured Ir sites (AD-HN-Ir) in the OER working conditions to successfully provide the atomically dispersed Ir electrocatalyst with ultrahigh electrochemical acidic OER activity. Using in-situ synchrotron radiation infrared and X-ray absorption spectroscopies, we directly observe that one oxygen atom is formed at the Ir active site with an O-hetero-Ir-N4 structure as a more electrophilic active centre in the experiment, which effectively promotes the generation of key *OOH intermediates under working potentials; this process is favourable for the dissociation of H2O over Ir active sites and resistance to over-oxidation and dissolution of the active sites. The optimal AD-HN-Ir electrocatalyst delivers a large mass activity of 2860 A gmetal−1 and a large turnover frequency of 5110 h−1 at a low overpotential of 216 mV (10 mA cm−2), 480–510 times larger than those of the commercial IrO2. More importantly, the AD-HN-Ir electrocatalyst shows no evident deactivation after continuous 100 h OER operation in an acidic medium.

The development of noble-metal-free, acid-compatible oxygen electrocatalysts and monitoring their active sites’ evolution under working conditions are crucial for global renewable energy storage and conversion. Here, we present a new type of hetero-N-coordinated Co (HNC-Co) single sites, with Co active centers bonding to hetero pyridinic- and amino-N ligands, as an efficient oxygen evolution reaction (OER) electrocatalyst in an acidic medium. The atomically dispersed HNC-Co electrocatalyst could effectively oxidize water at a quite low overpotential of 265 mV at 10 mA cm–2 in 0.5 M H2SO4 solution with an ultrahigh turnover frequency of 2.8 s–1 and a huge mass activity of 7.6 A mg–1, ∼80–240 times that of commercial IrO2. By using operando synchrotron infrared spectroscopy, a potential-driven active site evolution of H2N–(*O–Co)–N4 is observed for the first time during the OER process, which greatly promotes the surface oxo-species transformation for efficient acidic OER catalysis.