Molecular hydrogen evolution catalysts (HECs) are synthetically tunable and often exhibit high activity, but they are also hampered by stability concerns and practical limitations associated with their use in the homogeneous phase. Their incorporation as integral linker units in metal–organic frameworks (MOFs) can remedy these shortcomings. Moreover, the extended three-dimensional structure of MOFs gives rise to high catalyst loadings per geometric surface area. Herein, we report a new MOF that exclusively consists of cobaloximes, a widely studied HEC, that act as metallo-linkers between hexanuclear zirconium clusters. When grown on conducting substrates and under applied reductive potential, the cobaloxime linkers promote electron transport through the film as well as function as molecular HECs. The obtained turnover numbers are orders of magnitude higher than those of any other comparable cobaloxime system, and the molecular integrity of the cobaloxime catalysts is maintained for at least 18 h of electrocatalysis. Being one of the very few hydrogen evolving electrocatalytic MOFs based on a redox-active metallo-linker, this work explores uncharted terrain for greater catalyst diversity and charge transport pathways.

The integration of molecular catalysts with low‐cost, solid light absorbers presents a promising strategy to construct catalysts for the generation of solar fuels. Here, we report a photocatalyst for CO₂ reduction that consists of a polymeric cobalt phthalocyanine catalyst (CoPPc) coupled with mesoporous carbon nitride (mpg‐CN_x) as the photosensitizer. This precious‐metal‐free hybrid catalyst selectively converts CO₂ to CO in organic solvents under UV/Vis light (AM 1.5G, 100 mW cm⁻², λ>300 nm) with a cobalt‐based turnover number of 90 for CO after 60 h. Notably, the photocatalyst retains 60 % CO evolution activity under visible light irradiation (λ>400 nm) and displays moderate water tolerance. The in situ polymerization of the phthalocyanine allows control of catalyst loading and is key for achieving photocatalytic CO₂ conversion.

Ni‐deposited mesoporous graphitic carbon nitride (Ni‐mpg‐CN_x) is introduced as an inexpensive, robust, easily synthesizable and recyclable material that functions as an integrated dual photocatalytic system. This material overcomes the need of expensive photosensitizers, organic ligands and additives as well as limitations of catalyst deactivation in the existing photo/Ni dual catalytic cross‐coupling reactions. The dual catalytic Ni‐mpg‐CN_x is demonstrated for C–O coupling between aryl halides and aliphatic alcohols under mild condition. The reaction affords the ether product in good‐to‐excellent yields (60–92 %) with broad substrate scope, including heteroaryl and aryl halides bearing electron‐withdrawing, ‐donating and neutral groups. The heterogeneous Ni‐mpg‐CN_x can be easily recovered from the reaction mixture and reused over multiple cycles without loss of activity. The findings highlight exciting opportunities for dual catalysis promoted by a fully heterogeneous system.

Electrolyzers combining CO ₂ reduction (CO ₂ R) with organic substrate oxidation can produce fuel and chemical feedstocks with a relatively low energy requirement when compared to systems that source electrons from water oxidation. Here, we report an anodic hybrid assembly based on a (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) electrocatalyst modified with a silatrane‐anchor ( STEMPO ), which is covalently immobilized on a mesoporous indium tin oxide ( meso ITO) scaffold for efficient alcohol oxidation (AlcOx). This molecular anode was subsequently combined with a cathode consisting of a polymeric cobalt phthalocyanine on carbon nanotubes to construct a hybrid, precious‐metal‐free coupled AlcOx–CO ₂ R electrolyzer. After three‐hour electrolysis, glycerol is selectively oxidized to glyceraldehyde with a turnover number (TON) of ≈1000 and Faradaic efficiency (FE) of 83 %. The cathode generated a stoichiometric amount of syngas with a CO:H ₂ ratio of 1.25±0.25 and an overall cobalt‐based TON of 894 with a FE of 82 %. This prototype device inspires the design and implementation of nonconventional strategies for coupling CO ₂ R to less energy demanding, and value‐added, oxidative chemistry.