Synthesis of Densely Packaged, Ultrasmall Pt⁰₂ Clusters within a Thioether‐Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Temperature

Abstract

The gram-scale synthesis, stabilization, and characterization of well-defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X-ray snapshots of Pt clusters, homogenously distributed and densely packaged within the channels of a metal-organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal clusters in solids for technically easier, cheaper, and dramatically less-dangerous industrial reactions.

ZD2‐Engineered Gold Nanostar@Metal‐Organic Framework Nanoprobes for T1‐Weighted Magnetic Resonance Imaging and Photothermal Therapy Specifically Toward Triple‐Negative Breast Cancer

“…Nanoscale MOFs are regarded as ideal nanoprobes for biomedical applications . However, in order to achieve multifunctional theranostic applications, it is desirable to synthesize MOF‐based nanocomposites by incorporating metal nanoparticles within MOF . As a typical kind of metal nanomaterial, gold nanoparticles (AuNPs) show excellent performances in surface enhanced Raman scattering imaging, photoacoustic imaging, and photothermal therapy (PTT), and are expected to have better theranostic performance by combining with MOFs.…”

Confined Pt11+ Water Clusters in a MOF Catalyze the Low‐Temperature Water–Gas Shift Reaction with both CO2 Oxygen Atoms Coming from Water

“…This striking result can only be explained by the incorporation of two water molecules in the final CO 2 product. One is tempted to think that as crambling of the CO and water oxygen atom occurs.However,GC-MS shows < 1% of isotopically labelled C 18 Oi nt he reaction atmosphere.Indeed, kinetics with 10 times excess of CO respect to H 2 18 Oshow that C 18 O 2 and regular H 2 Oare still formed from the very beginning of the reaction, and as the reaction progresses,r egular CO 2 and mixed CO 18 Oa re formed statistically,d epending on the ratio H 2 O/H 2 O 18 in the media. Thef inal mixture contains > 50 %o fi sotopically labelled C 18 O 2 ,amuch higher proportion than expected for at hermodynamic mixture at these reaction conditions (iso-…”

“…However,t he CO adsorption isotherms are different for 2 and 3.The CO uptake is higher for 2 but irreversible ( Figure S18), which contrasts with the reversible adsorption isotherm for 3.C OF T-IR shows that CO adsorbs at À178 8 8Conthe available Pt + sites of 2 (Pt 2+ )and 3 (Pt 1+ )with different intensity (Figure S19), and that Pt 1+ -CO signals in 3 disappear when heating to give CO 2 as ap roduct, while any adventitious Pt 0 species do not react. 0.8 nm) of zeolite KLTA [17] and mordenite (MOR), ar elated MOF structure with Pt 0 dimers, [18] and MOF 2,s howed small (TOF < 5h À1 )o rn o activity up to 150 8 8C. [15] While it is true that Figure S19 also indicates that some Pt 0 can be present or formed during reaction conditions,a ll the data shown above soundly point to the major Pt species in the MOF,t hat is,P t 1+ ,a st he only responsible for the catalytic activity.…”

Blaise‐Pascal‐Medaillen: A. Corma und P. Samorì / Kavli‐Preis: E. Charpentier, J. Doudna und V. Šikšnys

“…Insbesondere beschäftigt er sich mit Synthese und Anwendungen von Zeolithkatalysatoren. In ChemSusChem berichtete er über Hafnium‐organische Gerüste als Katalysatoren für Transferhydrierungen, und in der Angewandten Chemie über die katalytische Aktivität von Pt 0 2 ‐Clustern in einem Metall‐organischen Gerüst . Corma gehört den internationalen Beiräten von Angewandter Chemie , ChemSusChem und The Chemical Record an.…”