A modular approach for the synthesis of highly ordered porous and chiral auxiliary (Evans auxiliary) decorated metal–organic frameworks is developed. Our synthesis strategy, which uses known porous structures as model materials for incorporation of chirality via linker modification, can provide access to a wide range of porous materials suitable for enantioselective separation and catalysis. Chiral analogues of UMCM-1 have been synthesized and investigated for the enantioseparation of chiral compounds in the liquid phase and first promising results are reported.

A detailed investigation of the influence of operating temperature on the electrochemical reduction of CO₂ to formate at tin oxide loaded gas diffusion electrodes (GDEs). Ambient pressure electrolysis is performed between 20 and 70 °C with a focus on maximizing current density and energy efficiency while maintaining an average formate faradaic efficiency of at least 80 %. The best performance is achieved at a temperature of 50 °C, which allows a current density of 1000 mA cm⁻². Lower or higher temperatures both show an increased hydrogen evolution at said current density. Further investigation of CO₂ transport limitation revealed a minimum at 50 °C, which is explained by the opposing influence of temperature on CO₂ diffusion coefficients and solubility. This explanation is supported by an estimate of the current density at which hydrogen evolution starts to increase based on the flooded agglomerate model. Long‐term operation for 24 h also revealed an optimum temperature of 50 °C, which helps to suppress the increasing rate of hydrogen evolution and with that a mechanical degradation of the GDE.

2D metal–organic‐framework (MOF) based composites have emerged as promising candidates for electrocatalysis due to their high structural flexibility and fully exposed active sites. Herein, a freestanding metal–organic layer (MOL) with a 2D kgd (kagome dual) lattice was constructed with abundant surface oxygenate groups serving as anchoring sites to immobilize diverse guests. Taking Bi as an example, tetragonal Bi₂O₃ nanowires can be uniformly grown on MOLs after solvothermal treatment, the structural evolution of which was followed by ex situ electron microscopy. The as‐prepared Bi₂O₃/MOL exhibits excellent CO₂ electroreduction activity towards formate reaching a specific current of 2.3 A mg_Bi⁻¹ and Faradaic efficiencies of over 85 % with a wide potential range from −0.87 to −1.17 V, far surpassing Bi₂O₃/UiO (a 3D Zr₆‐oxo based MOF) and Bi₂O₃/AB (Acetylene Black). Such a post‐synthetic modification strategy can be flexibly extended to develop versatile MOL composites, highlighting the superiority of optimizing MOL‐based composites for electrocatalysis.

A bimetallic triply fused copper(II) porphyrin complex (1) was prepared, comprising two monomeric porphyrin units linked through β–β, meso–meso, β′–β′ triple covalent linkages and exhibiting remarkable catalytic activity for the electrochemical hydrogen evolution reaction in comparison to the analogous monomeric copper(II) porphyrin complex (2). Electrochemical investigations in the presence of a proton source (trifluoroacetic acid) confirmed that the catalytic activity of the fused metalloporphyrin occurred at a significantly lower overpotential (≈320 mV) compared to the non‐fused monomer. Controlled potential electrolysis combined with kinetic analysis of catalysts 1 and 2 confirmed production of hydrogen, with 96 and 71 % faradaic efficiencies and turnover numbers of 102 and 18, respectively, with an observed rate constant of around 10⁷ s⁻¹ for the dicopper complex. The results thus firmly establish triply fused porphyrin ligands as outstanding candidates for generating highly stable and efficient molecular electrocatalysts in combination with earth‐abundant 3d transition metals.