The stabilization of transition metals as isolated centres on suitably tailored carriers with high density is crucial to exploit the technical potential of single-atom heterogeneous catalysts, enabling their maximized productivity in industrial reactors. Wet-chemical methods are best suited for practical applications due to their amenability to scale up. However, achieving single-atom dispersions at metal contents above 2 wt.% remains challenging. We introduce a versatile approach combining impregnation and two-step annealing to synthesize ultra-high-density single-atom catalysts (UHD-SACs) with unprecedented metal contents up to 23 wt.% for 15 metals on chemically-distinct carriers. Translation to an automated protocol demonstrates its robustness and provides a path to explore virtually unlimited libraries of mono or multimetallic catalysts. At the molecular level, characterization of the synthesis mechanism through experiments and simulations shows that controlling the bonding of metal precursors with the carrier via stepwise ligand removal prevents their thermally-induced aggregation into nanoparticles, ensuring atomic dispersion in the resulting UHD-SACs. The catalytic bene ts of UHD-SACs are demonstrated for the electrochemical reduction of CO 2 to CO over NiN 4 motifs on carbon.

The carbonylation of carbenes through catalytic cycles is highly desirable due to the importance of ketene-mediated reactions in organic synthesis. In this investigation, a highly efficient and mild catalytic approach toward ketene intermediates has been developed based on Pd-catalyzed carbonylation of diazo compounds with CO. When α-diazocarbonyl compounds or N-tosylhydrazone salts are heated in the presence of a palladium catalyst under atmospheric pressure of CO, ketene intermediates are formed in situ, where they undergo further reactions with various nucleophiles such as alcohols, amines, or imines. The Pd-catalyzed tandem carbonylation-Staudinger cycloaddition gives β-lactam derivatives in good yields with excellent trans diastereoselectivity. The results from DFT calculation on the reaction mechanism suggest that Pd is involved in the [2 + 2] cycloaddition process and affects the diastereoselectivity of the β-lactam products by assisting isomerization of the addition intermediate. On the other hand, the acylketenes generated from the Pd-catalyzed carbonylation of α-diazoketones react with imines in a formal [4 + 2] cycloaddition manner to afford 1,3-dioxin-4-one derivatives. This straightforward carbonylation provides a new approach toward highly efficient catalytic generation of ketene species under mild conditions.

Single-atom catalysts (SACs) with magnetic elements as the active center have been widely exploited for efficient electrochemical conversions. Understanding the catalytic role of spin, and thus modulating the spin density of a single-atom center, is of profound fundamental interest and technological impact. Here, we synthesized ferromagnetic single Co atom catalysts on TaS2 monolayers (Co1/TaS2) as a model system to explore the spin–activity correlation for the oxygen evolution reaction (OER). A single Co atom adsorbed at the hollow site (CoHS) with spin-polarized electronic states serves as the active site for OER, whose spin density can be regulated by its neighboring single Co site via tuning the Co loading. Both experimental and theoretical results reveal the spin density-dependent OER activity that an optimal spin density of CoHS can be achieved with a neighboring hetero-single CoTa site (substitution of Ta by Co) for a superior OER performance, in contrast to a homo-single CoHS site, which creates an excessive spin density over vicinal CoHS. An optimized spin density of CoHS results in an optimal binding energy of oxygen species for the OER. Establishing the spin–activity correlation in SACs may create a descriptor for designing efficient magnetic SACs for renewable energy conversions.

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