Modulated zirconium metal–organic framework UiO‐66 is shown to catalyze the isomerization of d‐glucose to d‐fructose in alcohol media. Fructose selectivity can change depending on solvent choice. We hypothesize that the difference in selectivity is related to a combined effect of adsorption and solvation effects, which may lead to the high formation of alkylglucosides in depletion of fructose if methanol or ethanol are used. A fructose selectivity of 72 % at 82 % glucose conversion in 1‐PrOH was achieved. The reaction mechanism was investigated using nuclear magnetic resonance spectroscopy. We demonstrate that UiO‐66 isomerizes glucose to fructose through an intramolecular C2–C1 hydride transfer. In addition, we show that modulated UiO‐66 is a highly active and stable catalyst at the reaction conditions, showing great potential for other sugar reactions.

Ruthenium (Ru) is the one of the most promising catalysts for polyolefin hydrogenolysis. Its performance varies widely with the support, but the reasons remain unknown. Here, we introduce a simple synthetic strategy (using ammonia as a modulator) to tune metal-support interactions and apply it to Ru deposited on titania (TiO2). We demonstrate that combining deuterium nuclear magnetic resonance spectroscopy with temperature variation and density functional theory can reveal the complex nature, binding strength, and H amount. H2 activation occurs heterolytically, leading to a hydride on Ru, an H+ on the nearest oxygen, and a partially positively charged Ru. This leads to partial reduction of TiO2 and high coverages of H for spillover, showcasing a threefold increase in hydrogenolysis rates. This result points to the key role of the surface hydrogen coverage in improving hydrogenolysis catalyst performance.

Patterning metal-organic frameworks (MOFs) at submicrometer scale is a crucial yet challenging task for their integration in miniaturized devices. Here we report an electron beam (e-beam) assisted, bottom-up approach for patterning of two MOFs, zeolitic imidazolate frameworks (ZIF), ZIF-8 and ZIF-67. A mild pretreatment of metal oxide precursors with linker vapor leads to the sensitization of the oxide surface to e-beam irradiation, effectively inhibiting subsequent conversion of the oxide to ZIFs in irradiated areas, while ZIF growth in non-irradiated areas is not affected. Well-resolved patterns with features down to the scale of 100 nm can be achieved. This developer-free, all-vapor phase technique will facilitate the incorporation of MOFs in micro- and nanofabrication processes.

Vapor phase ligand treatment (VPLT) of 2‐aminobenzimidazole (2abIm) for 2‐methylimidazole (2mIm) in ZIF‐8 membranes prepared by two different methods (LIPS: ligand induced permselectivation and RTD: rapid thermal deposition) results in a notable shift of the molecular level cut‐off to smaller molecules establishing selectivity improvements from ca. 1.8 to 5 for O2/N2; 2.2 to 32 for CO2/CH4; 2.4 to 24 for CO2/N2; 4.8 to 140 for H2/CH4 and 5.2 to 126 for H2/N2. Stable (based on a one‐week test) oxygen‐selective air separation performance at ambient temperature, 7 bar(a) feed, and 1 bar(a) sweep‐free permeate with a mixture separation factor of 4.5 and oxygen flux of 2.6×10−3 mol m−2 s−1 is established. LIPS and RTD membranes exhibit fast and gradual evolution upon a 2abIm‐VPLT, respectively, reflecting differences in their thickness and microstructure. Functional reversibility is demonstrated by showing that the original permeation properties of the VPLT‐LIPS membranes can be recovered upon 2mIm‐VPLT.