One-pot three-component regioselective azide-alkyne cycloadditions are central reactions for synthesizing pharmaceuticals and fine chemicals and are also applied for in vivo metabolic labeling biotechnology. Homogeneous catalysts based on copper species coordinated with ancillary ligands are regularly used to perform this reaction, offering superior catalytic activity and selectivity compared to conventional heterogeneous counterparts based on supported copper nanoparticles. However, the challenge of catalyst recovery limits the use of these homogeneous compounds in many large-scale applications. In this work, we report the high catalytic performance of a family of Cu-based single-atom catalysts for triazole synthesis, with an emphasis on the fundamental understanding of the structure and function of the catalyst. The catalysts were prepared via tricyanomethanide polymerization to create a joint electronic structure where the mesoporous graphitic carbon nitride carrier acts as a ligand for the atomically dispersed copper species. The material properties and the precise metal location/coordination (i.e., deposited in the heptazine pore of carbon nitride, substituted in the framework of carbon nitride, hosted in a vacancy, or entrapped in sandwich-like arrangement) were characterized through a battery of spectroscopic and theoretical methods. The catalysts were employed in the synthesis of 1,2,3-triazoles employing azide-alkyne click reaction under base-free conditions. The single-atom Cu catalysts demonstrated improved activity and selectivity compared to the homogeneous reference catalyst. Density functional theory calculations corroborated the results and showed that the reaction proceeds through a barrier given by the activation of the acetylenic moiety on Cu₁. The activity of this step was primarily affected by the coordination of the metal with the support. Therefore, understanding the metal coordination in single-atom catalysts is critical to further optimizing single-atom catalysts and greening synthetic chemistry.

Transition metal oxides often undergo dynamic surface reconstruction under oxygen evolution reaction conditions to form the active state, which differs in response to the electrolyte pH. The resulting pH dependency of catalytic activity is commonly observed but poorly understood. Herein we track Co oxidation state changes at different pH-directed (hydr)oxide/electrolyte interfaces using operando X-ray absorption spectroscopy characterizations. Combined with in situ electrochemical analyses, we establish correlations between Co redox dynamics, the flat band potential and Co oxidation state changes to explain the pH dependency of the oxygen evolution activity. Alkaline environments provide a low flat band potential that yields a low-potential Co redox transformation, which favours surface reconstruction. Neutral and acidic environments afford an anodic shift of the Co redox transformation that increases the catalytic overpotential. The larger overpotential in neutral environments is attributable to poor Co atom polarizability and slow Co oxidation state changes. These findings reveal that interfacial Co oxidation state changes directly determine the pH dependency of the oxygen evolution reaction activity.

The high temporal resolution in data acquisition, possible in the quick-scanning EXAFS (QEXAFS) mode of operation, provides new challenges in efficient data processing methods. Here a new approach is developed that combines an easy to use interactive graphical interface with highly optimized and fully parallelized Python-based routines for extracting, normalizing and interpolating oversampled time-resolved XAS spectra from a raw binary stream of data acquired during operando QEXAFS studies. The programs developed are freely available via a Github repository.