Yuzhen Chen

Bimetallic metal–organic frameworks are rationally synthesized as templates and employed for porous carbons with retained morphology, high graphitization degree, hierarchical porosity, high surface area, CoNx moiety and uniform N/Co dopant by pyrolysis. The optimized carbon with additional phosphorus dopant exhibits excellent electrocatalytic performance for the oxygen reduction reaction, which is much better than the benchmark Pt/C in alkaline media. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

The selectivity control toward aldehyde in the aromatic alcohol oxidation remains a grand challenge using molecular oxygen under mild conditions. In this work, we designed and synthesized Pt/PCN-224(M) composites by integration of Pt nanocrystals and porphyrinic metal–organic frameworks (MOFs), PCN-224(M). The composites exhibit excellent catalytic performance in the photo-oxidation of aromatic alcohols by 1 atm O2 at ambient temperature, based on a synergetic photothermal effect and singlet oxygen production. Additionally, in opposition to the function of the Schottky junction, injection of hot electrons from plasmonic Pt into PCN-224(M) would lower the electron density of the Pt surface, which thus is tailorable for the optimized catalytic performance via the competition between the Schottky junction and the plasmonic effect by altering the light intensity. To the best of our knowledge, this is not only an unprecedented report on singlet oxygen-engaged selective oxidation of aromatic alcohols to aldehydes but also the first report on photothermal effect of MOFs.

Metal nanoparticles (NPs) stabilized by metal–organic frameworks (MOFs) are very promising for catalysis, while reports on their cooperative catalysis for a cascade reaction have been very rare. In this work, Pd NPs incorporated into a MOF, MIL-101, have jointly completed a tandem reaction on the basis of MOF Lewis acidity and Pd NPs. Subsequently, ultrafine PdAg alloy NPs (∼1.5 nm) have been encapsulated into MIL-101. The obtained multifunctional PdAg@MIL-101 exhibits good catalytic activity and selectivity in cascade reactions under mild conditions, on the basis of the combination of host–guest cooperation and bimetallic synergy, where MIL-101 affords Lewis acidity and Pd offers hydrogenation activity while Ag greatly improves selectivity to the target product. As far as we know, this is the first work on bimetallic NP@MOFs as multifunctional catalysts with multiple active sites (MOF acidity and bimetallic species) that exert respective functions and cooperatively catalyze a one-pot cascade reaction.

A new strategy to pre-incorporate metal precursors followed by their in situ reduction is established to prepare tiny core-shell nanoparticles (NPs) stabilized by a metal-organic framework (MOF). The obtained Pd@Co core-shell NPs of ∼2.5 nm confined in the pores of a mesoporous MOF, MIL-101, exhibit synergistic and superior catalytic performance in hydrolytic dehydrogenation of NH3 BH3 under mild conditions compared to their monometallic and alloy counterparts as well as Pd@Co NPs located on a MOF surface.