Metal–organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds

Escamilla, Paula; Guerra, Walter Damian; Leyva‐Pérez, Antonio; Armentano, Donatella; Ferrando‐Soria, Jesús; Pardo, Emilio

doi:10.1039/d2cc05686k

Cited by 9 publications

(2 citation statements)

References 118 publications

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“…Metal-organic frameworks (MOFs) are porous crystalline materials with extremely high surface areas 30 . They also exhibit a very interesting host-guest chemistry 31 -a direct consequence of their functional empty space-that permits their use as chemical nanoreactors to produce/stabilize unprecedented metal chemical species 32 . Following this approach, our groups have recently reported the formation of well-defined palladium 33 and platinum 34 The gold atoms are stabilized by interactions involving oxygen atoms from the oxamate moieties, belonging to the MOF core, and delimiting the walls of the MOF at a distance of 2.91 Å.…”

Section: Synthesis and Characterization Of Pd 1 Au 1 @1mentioning

confidence: 99%

A MOF-supported Pd1–Au1 dimer catalyses the semihydrogenation reaction of acetylene in ethylene with a nearly barrierless activation energy

Ballesteros-Soberanas,

Martín,

Bacic

et al. 2024

Nat Catal

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The removal of acetylene from ethylene streams is key in industry for manufacturing polyethylene. Here we show that a well-defined Pd1–Au1 dimer, anchored to the walls of a metal–organic framework (MOF), catalyses the selective semihydrogenation of acetylene to ethylene with ≥99.99% conversion (≤1 ppm of acetylene) and >90% selectivity in extremely rich ethylene streams (1% acetylene, 89% ethylene, 10% H2, simulated industrial front-end reaction conditions). The reaction proceeds with an apparent activation energy of ∼1 kcal mol–1, working even at 35 °C, and with operational windows (>100 °C) and weight hourly space velocities ($$66{,}000\,{\mathrm{ml}}\,{\mathrm{g}}^{-1}_{\mathrm{cat}}\,{\mathrm{h}}^{-1}$$ 66 , 000 ml g cat − 1 h − 1 ) within industrial specifications. A combined experimental and computational mechanistic study shows the cooperativity between both atoms, and between atoms and support, to enable the barrierless semihydrogenation of acetylene.

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Section: Synthesis and Characterization Of Pd 1 Au 1 @1mentioning

confidence: 99%

A MOF-supported Pd1–Au1 dimer catalyses the semihydrogenation reaction of acetylene in ethylene with a nearly barrierless activation energy

Ballesteros-Soberanas,

Martín,

Bacic

et al. 2024

Nat Catal

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“…1b). Since one of the main applications of MNPs is catalysis, 16,17 we next use the time-resolved encapsulation method to analyse the effect of the injection time on the performance of the resulting catalyst associated with changes in reactant accessibility and/or the chemical nature of the MNP surface. 18 Our results reveal changes in conversion, selectivity and catalyst recyclability for the Au-catalyzed cyclotrimerization of propargyl esters 19 and the hydrochlorination of alkynes, 20 confirming the potential of controlling the injection of nanoparticles at adjustable times for composites with superior catalytic performance.…”

Section: Introductionmentioning

confidence: 99%

Time-resolved control of nanoparticle integration in titanium-organic frameworks for enhanced catalytic performance

Fernández-Conde,

Zheng,

Mon

et al. 2024

Chem. Sci.

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Engineering Metal‐MOF Interfaces for Selective CO₂ Hydrogenation to Methanol

Ramos‐Fernández,

Velisoju,

Gascon

et al. 2024

Chemistry A European J

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The hydrogenation of CO2 to methanol is a promising pathway toward sustainable fuel production and carbon recycling. A key factor in the efficiency of this process lies in the interaction between the metal catalyst and its support. Metal‐Organic Frameworks (MOFs) have emerged as highly effective platforms due to their tunable structures, large surface areas, and ability to form stable interfaces with single–atom metals or metal nanoparticles. These metal‐MOF interfaces are crucial for stabilizing active sites, preventing sintering, and enhancing catalytic performance. In this concept paper, we explore the role of these interfaces in promoting CO2 hydrogenation, focusing on Cu‐Zn, Cu‐Zr, and Zn‐Zr interfaces. The formation of strong interactions between metal sites and MOF nodes enables precise control over the dispersion and electronic environment of the active species, significantly improving methanol selectivity and long‐term stability. By analyzing recent advancements in MOF‐supported catalysts, this work highlights the concept of engineered metal‐MOF interfaces to drive the development of next‐generation catalysts for efficient methanol synthesis from CO2.

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Metal–organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds

Abstract: Since the emergence of metal-organic frameworks (MOFs), a myriad of thrilling properties and applications, in a wide range of fields, have been reported for these materials, which mainly arise from...

Cited by 9 publications

References 118 publications

A MOF-supported Pd1–Au1 dimer catalyses the semihydrogenation reaction of acetylene in ethylene with a nearly barrierless activation energy

A MOF-supported Pd1–Au1 dimer catalyses the semihydrogenation reaction of acetylene in ethylene with a nearly barrierless activation energy

Time-resolved control of nanoparticle integration in titanium-organic frameworks for enhanced catalytic performance

Engineering Metal‐MOF Interfaces for Selective CO₂ Hydrogenation to Methanol

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