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This work describes the first generalizable method to modify various metal–organic framework (MOF) surfaces with polyimide, polysulfone, polycarbonate, and polymer of intrinsic microporosity‐1 (PIM‐1). The method first utilizes electrostatic adsorption to rapidly decorate positively charged MOF surfaces with a layer of negatively charged metal‐organic nanocapsule, PgC5Cu. After mixing with the polymer, the copper open metal sites on PgC5Cu can coordinatively crosslink the polar functional groups on the surface polymer upon thermal activation thereby resulting in the immobilization of a uniform sub‐10 nm polymer coating. We quantitatively analyzed the distribution of free path spacing between MOF particles and demonstrated that when the surface polymer matches the matrix polymer, the MOF dispersion was not only visually improved but also found to align perfectly with a theoretically predicted ideal dispersion model where no aggregation driving force was present. [ABSTRACT FROM AUTHOR]

Improving catalytic activity without loss of catalytic stability is one of the core goals in search of low‐iridium‐content oxygen evolution electrocatalysts under acidic conditions. Here, we synthesize a family of 66 SrBO3 perovskite oxides (B=Ti, Ru, Ir) with different Ti : Ru : Ir atomic ratios and construct catalytic activity‐stability maps over composition variation. The maps classify the multicomponent perovskites into chemical groups with distinct catalytic activity and stability for acidic oxygen evolution reaction, and highlights a chemical region where high catalytic activity and stability are achieved simultaneously at a relatively low iridium level. By quantifying the extent of hybridization of mixed transition metal 3d‐4d‐5d and oxygen 2p orbitals for multicomponent perovskites, we demonstrate this complex interplay between 3d‐4d‐5d metals and oxygen atoms in governing the trends in both activity and stability as well as in determining the catalytic mechanism involving lattice oxygen or not. [ABSTRACT FROM AUTHOR]

Single‐atom catalysts have drawn great attention, especially in electrocatalysis. However, most of previous works focus on the enhanced catalytic properties via improving metal loading. Engineering morphologies of catalysts to facilitate mass transport through catalyst layers, thus increasing the utilization of each active site, is regarded as an appealing way for enhanced performance. Herein, we design an overhang‐eave structure decorated with isolated single‐atom iron sites via a silica‐mediated MOF‐templated approach for oxygen reduction reaction (ORR) catalysis. This catalyst demonstrates superior ORR performance in both alkaline and acidic electrolytes, comparable to the state‐of‐the‐art Pt/C catalyst and superior to most precious‐metal‐free catalysts reported to date. This activity originates from its edge‐rich structure, having more three‐phase boundaries with enhanced mass transport of reactants to accessible single‐atom iron sites (increasing the utilization of active sites), which verifies the practicability of such a synthetic approach. [ABSTRACT FROM AUTHOR]

Antiperovskite Co3InC0.7N0.3 nanomaterials with highly enhanced oxygen reduction reaction (ORR) performance were prepared by tuning nitrogen contents through a metal–organic framework (MOF)‐derived strategy. The nanomaterial surpasses all reported noble‐metal‐free antiperovskites and even most perovskites in terms of onset potential (0.957 V at J=0.1 mA cm−2) and half‐wave potential (0.854 V). The OER and zinc–air battery performance demonstrate its multifunctional oxygen catalytic activities. DFT calculation was performed and for the first time, a 4 e− dissociative ORR pathway on (200) facets of antiperovskite was revealed. Free energy studies showed that nitrogen substitution could strengthen the OH desorption as well as hydrogenation that accounts for the enhanced ORR performance. This work expands the scope for material design via tailoring the nitrogen contents for optimal reaction free energy and hence performance of the antiperovskite system. [ABSTRACT FROM AUTHOR]