The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd₄ clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd₄ clusters retain their catalytic activity in repeated batch and flow reactions (>20 cycles). Our findings demonstrate how this synthetic approach may now instruct the future design of heterogeneous catalysts with advantageous reaction capabilities for other important processes.

Purification of methane from other light hydrocarbons in natural gas is a topic of intense research due to its fundamental importance in the utilization of natural gas fields. Porous materials have emerged as excellent alternative platforms to conventional cryogenic methodologies to perform this task in a cost- and energy-efficient manner. Here we report a new family of isoreticular chiral MOFs, prepared from oxamidato ligands derived from natural amino acids l-alanine, l-valine and l-leucine, where, by increasing the length of the alkyl residue of the amino acid, the charge density of the MOF's channels can be tuned (1 > 2 > 3), decreasing the adsorption preference towards methane over light hydrocarbons thus improving this purification process. The validity of our rational design strategy has been proved by a combination of single-component adsorption isotherms, adsorption kinetics of CH₄, C₂H₆, C₃H₈ and n-C₄H₁₀, and breakthrough experiments of binary CH₄/C₂H₆ and CH₄/C₃H₈ mixtures.