Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe, Cr or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

Here, the synthesis of a wafer‐scale ultrathin 2D imine polymer (2DP) film with controllable thickness from simple benzene‐1,3,5‐tricarbaldehyde (BTA) and p‐phenylenediamine (PDA) building blocks is reported using a Schiff base polycondensation reaction at the air–water interface. The synthesized freestanding 2DP films are porous, insulating, and more importantly, covalently linked, which is ideally suited for nonvolatile memristors that use a conductive filament mechanism. These devices exhibit excellent switching performance with high reliability and reproducibility, with on/off ratios in the range of 102 to 105 depending on the thickness of the film. In addition, the endurance and data retention capability of 2DP‐based nonvolatile resistive memristors are up to 200 cycles and 8 × 104 s under constant voltage stress at 0.1 V. The intrinsic flexibility of the covalent organic polymer enables the fabrication of a flexible memory device on a polyimide film, which exhibits as reliable memory performance as that on the rigid substrate. Moreover, the 2DP‐based memory device shows outstanding thermal stability and organic solvent resistance, which are desirable properties for applications in wearable devices.