Catalytic mechanisms articles from across Nature Portfolio

The stereospecific Z/E isomerization of tetrasubstituted alkenes remains underdeveloped, thus lacking in a stereodivergent synthesis of axially chiral alkenes. Here, authors report the atroposelective synthesis of tetrasubstituted alkene analogues by asymmetric allylic substitution-isomerization, followed by the photocatalyzed Z/E isomerization.

The poisoning of single-atom catalysts hampers their performance. Here, the authors propose Au nanoparticles as an antidote for poisoned Au single-atom catalysts, with trace addition shown to reinforce and sustain propylene epoxidation.

Catalyst activation commonly occurs during reactions. This study demonstrates that the surface’s active structure in nitride catalysts during the reverse water gas-shift reaction varies with the partial pressure of reaction products, resulting in enhanced catalytic activity through positive feedback between catalytic activity and the evolution of MoNx’s active structure.

Heterogeneous catalysis that occurs when the anodic and cathodic reactions are short-circuited in an appropriate electrolyte is conceptualized as mixed-potential-driven catalysis, however, its theoretical framework remains underexplored. Here, the authors propose the overpotentials as the driving force of the catalysis and extend Prigogine’s theory to formulate the kinetic equations for the energy conversion from the cathodic and anodic half-reactions into overpotentials, by formation of a mixed potential determined by the catalytic activity.

Establishing optimal metal-support interactions is crucial for creating efficient catalysts for water splitting. Here, stable Ti–O–Ru interface formation and minimal work function difference between Ru nanoparticles and non-stoichiometric Ti4O7 lead to exceptional bifunctional activity of Ru/Ti4O7 for both HER and OER across pH-universal environments, maintaining stable operation for 500 h.

While skeletal editing stands as a powerful approach for simplifying synthetic procedures and obtaining complex molecules, viable methodologies remain limited. Now, a smart photoredox protocol, involving the insertion of carbon atoms into the indene core, gives access to a wide library of functionalized naphthalenes.

Ciro Romano, Jack I. Mansell, and David J. Procter have explored the versatility and selectivity of samarium diiodide, and its use as a radical relay catalyst.

A self-driving lab, called Fast-Cat, is developed for the rapid, autonomous Pareto-front mapping of homogeneous catalysts in high-pressure, high-temperature gas–liquid reactions. The efficacy of Fast-Cat was demonstrated in performing Pareto-front mappings of phosphorus-based ligands for the hydroformylation of olefins.

A deeper understanding of reaction mechanisms should lead to improvements in the selectivity of organic electrosynthesis methods. This approach has now been used to explain the role of magnesium diacetate in the Ag-electrocatalysed reductive coupling of sp³ organic chlorides with aldehydes or ketones with increased selectivity for the desired alcohol product.

Lignin contains both C–O and C–C bonds, where C–C bonds are highly resistant to cleavage. Now, a bifunctional catalyst enables the cleavage of the challenging C–C bonds in lignin to produce biofuels.