The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that highly crystalline porous solids, metal-organic frameworks, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known metal organic framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks, and for other applications.

We report the preparation and electrocatalytic performance of silver-containing gas diffusion electrodes (GDE) derived from a silver coordination polymer (Ag-CP). Layer-bylayer growth of the Ag-CP onto porous supports was applied to control Ag loading. Subsequent electro-decomposition of the Ag-CP resulted in highly selective (FECO > 90%) and stable CO2to-CO gas diffusion electrodes in aqueous CO2 electroreduction over a wide potential range, with jCO ≈ 30.2 mA cm −2 at −1 V vs RHE. To further explore the potential of this electrode preparation method, the MOF-mediated approach was transferred to a gas-fed flow electrolyzer for high-current density tests. The in-situ formed gas-diffusion electrode (GDE), with a remarkably low silver loading of 0.2 mg cm −2 , showed a peak performance of jCO ≈ 385 mA cm −2 at around −1.0 V vs RHE and stable operation with high FECO (> 96%) at jTotal = 300 mA cm −2 over a 4 h run. These results demonstrate that the MOF-mediated approach offers a facile route to manufacture uniformly dispersed Ag catalysts for CO2ER by eliminating the need for illdefined deposition steps (drop-casting etc.), while allowing control of the catalyst structure through self-assembly.

The tandem process of carbon dioxide hydrogenation to methanol and its conversion to hydrocarbons over mixed metal/metal oxide-zeotype catalysts is a promising path to CO2 valorization.

Solar‐driven methanation represents a potentially cost‐efficient and environmentally friendly route for the direct hydrogenation of CO2. Recently, photothermal catalysis, which involves the combination of both photochemical and thermochemical pathways, has emerged as a promising strategy for the production of solar fuels. For a photothermal catalyst to efficiently convert CO2 under illumination, in the absence of external heating, effective light harvesting, an excellent photothermal conversion and efficient active sites are required. Here, a new composite catalyst consisting of Ni nanoparticles supported on barium titanate that, under optimal reaction conditions, is able to hydrogenate CO2 to CH4 at nearly 100% selectivity with production rates as high as 103.7 mmol g–1 h–1 under both UV–visible and visible irradiation (production rate: 40.3 mmol g−1 h–1) is reported. Mechanistic studies suggest that reaction mostly proceeds through a nonthermal hot‐electron‐driven pathway, with a smaller thermal contribution.

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