Singlet Oxygen-Engaged Selective Photo-Oxidation over Pt Nanocrystals/Porphyrinic MOF: The Roles of Photothermal Effect and Pt Electronic State

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

Multifunctional PdAg@MIL-101 for One-Pot Cascade Reactions: Combination of Host–Guest Cooperation and Bimetallic Synergy in Catalysis

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

Multifunctional PdAg@MIL-101 for One-Pot Cascade Reactions: Combination of Host–Guest Cooperation and Bimetallic Synergy in Catalysis

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

Multifunctional PdAg@MIL-101 for One-Pot Cascade Reactions: Combination of Host–Guest Cooperation and Bimetallic Synergy in Catalysis

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

Hollow Metal–Organic Framework Nanospheres via Emulsion-Based Interfacial Synthesis and Their Application in Size-Selective Catalysis

Metal–organic frameworks (MOFs) represent an emerging class of crystalline materials with well-defined pore structures and hold great potentials in a wide range of important applications. The functionality of MOFs can be further extended by integration with other functional materials, e.g., encapsulating metal nanoparticles, to form hybrid materials with novel properties. In spite of various synthetic approaches that have been developed recently, a facile method to prepare hierarchical hollow MOF nanostructures still remains a challenge. Here we describe a facile emulsion-based interfacial reaction method for the large-scale synthesis of hollow zeolitic imidazolate framework 8 (ZIF-8) nanospheres with controllable shell thickness. We further demonstrate that functional metal nanoparticles such as Pd nanocubes can be encapsulated during the emulsification process and used for heterogeneous catalysis. The inherently porous structure of ZIF-8 shells enables encapsulated catalysts to show size-selective hydrogenation reactions