Molecular catalysts that combine high product selectivity and high current density for CO 2 electrochemical reduction to CO or other chemical feedstocks are urgently needed. While earth-abundant metal-based molecular electrocatalysts with high selectivity for CO 2 to CO conversion are known, they are characterized by current densities that are significantly lower than those obtained with solid-state metal materials. Here, we report that a cobalt phthalocyanine bearing a trimethyl ammonium group appended to the phthalocyanine macrocycle is capable of reducing CO 2 to CO in water with high activity over a broad pH range from 4 to 14. In a flow cell configuration operating in basic conditions, CO production occurs with excellent selectivity (ca. 95%), and good stability with a maximum partial current density of 165 mA cm −2 (at −0.92 V vs. RHE), matching the most active noble metal-based nanocatalysts. These results represent state-of-the-art performance for electrolytic carbon dioxide reduction by a molecular catalyst.

Four isomerically pure octasubstituted zinc phthalocyanines with variations in the attachment atom and positions of the substituents were selected for a systematic investigation of the effect of the substitution pattern on their electronic and spectroscopic properties. Effects which were investigated are the position, the electron donating and withdrawing properties, and the donating force of the substituent. The results are discussed and interpreted based on theoretical and experimental determination of the orbital levels. This work allows us to highlight which substitution patterns are the most suitable considering different common applications of phthalocyanines.

A combination of MS and computation on μ-nitrido bridged diiron complexes reveals H2O2 binding to the complex and generates an oxidant capable of oxidizing methane.

An entirely earth‐abundant chromophore‐relay water oxidation catalyst triad system, which is robust and efficient at neutral pH, is presented. The synthesis involves the coordination of a porphyrin derivative to a bridging Fe(CN)5 group, which is then reacted with Co ions to prepare a covalently linked chromophore–Prussian blue analogue assembly. Light‐driven water oxidation studies in the presence of an electron scavenger indicate that the triad is active and it maintains a steady activity for at least three hours. Transient absorption experiments and computational studies reveal that the Fe(CN)5 group is more than a linker as it takes part in electron‐transfer and co‐operates with porphyrin in the charge separation process.