Metal porphyrins and metal phthalocyanines (Pc) constitute a promising class of metal molecular catalysts (MMCs) for efficient CO₂-to-CO electrocatalytic conversion due to their well-defined molecular structures. How to adjust the local coordination and electronic environment of the metal center and enhance the molecular-level dispersion of the active components remains as great challenges for further improving the performance. Herein, a cobalt(II) Pc (CoPc)-COOH/carbon nanotube (CNT)-NH₂ hybrid catalyst was rationally designed by clicking the CoPc-COOH molecules onto the surface of CNT-NH₂ through amidation reaction. This novel hybrid catalyst exhibited the enhanced current density of 22.4 mA/cm² and CO selectivity of 91% at −0.88 V vs. reversible hydrogen electrode (RHE) in the CO₂ electroreduction, as compared with CoPc-COOH/CNT and CoPc/CNT samples. The superior activity was ascribed to the charge transfer induced by introduction of –COOH and –NH₂ functional groups to CoPc and CNT, respectively, facilitating the active centers of Co^I being generated at lower potentials, and leading to the highest turnover frequency (TOF) being obtained over the CoPc-COOH/CNT-NH₂ hybrid catalyst. The inherent directivity and saturability of covalent bonds formed via the amidation reaction ensure not only a higher density of Co active centers, but also an improved stability for CO₂ reduction reaction (CO₂RR). The present study represents an effective strategy for improving MMCs performance by molecular modulating of metal phthalocyanines on functionalized carbon substrates directed by click confinement chemistry.

Design and development of high-efficiency and durable oxygen evolution reaction (OER) electrocatalysts is crucial for hydrogen production from seawater splitting. Herein, we report the in situ electrochemical conversion of a nanoarray of Ni(TCNQ)₂ (TCNQ = tetracyanoquinodimethane) on graphite paper into Ni(OH)₂ nanoparticles confined in a conductive TCNQ nanoarray (Ni(OH)₂-TCNQ/GP) by anode oxidation. The Ni(OH)₂-TCNQ/GP exhibits high OER performance and demands overpotentials of 340 and 382 mV to deliver 100 mA·cm⁻² in alkaline freshwater and alkaline seawater, respectively. Meanwhile, the Ni(OH)₂-TCNQ/GP also demonstrates steady long-term electrochemical durability for at least 80 h under alkaline seawater.