Volume 5 Issue 6, June 2022

Supported subnanometre catalysts are atom efficient and possess unique properties, but their structure–activity relations are not well understood. Now it is possible to reveal their structure sensitivity by combining multimodal experiments and computations.

Rationalizing the difference in the catalytic properties within a group of materials is a challenging task. A method is now proposed that addresses this issue by predicting the activity and stability of platinum-based electrocatalysts from operando spectroscopic data.

The direct use of ammonia for asymmetric synthesis is highly sought after. Now, an efficient enantioselective carbene insertion into the N–H bond of ammonia has been developed, producing diverse valuable chiral α-amino acids.

The oxygen reduction reaction (ORR) plays a central role in electrochemistry for applications such as energy conversion and storage. This Review focuses on the fundamentals, technology and perspectives of ORR as an abiotic or biotic process at near neutral pH.

Structure sensitivity is an important property in catalysis, although its determination at the atomic cluster scale remains difficult. Here, the authors explore the reactivity of different palladium clusters with low nuclearity identifying the ideal Pd–Pd coordination number for the dehydrogenation of dodecahydro-N-ethylcarbazole.

Olefin metathesis is a powerful synthetic method that largely rests on the reactivity of molybdenum- and ruthenium-based catalysts, as alternative metals have not yet been successfully substituted. Here the authors engineer an iron catalyst to effectively perform the stereoselective ring-opening metathesis polymerization of norbornene.

The high cost of Pt severely limits fuel cell deployment, but alternative Pt-free catalysts suffer from a low activity and, especially, durability. Now, a low-Pt-content catalyst consisting of Pt and Fe single atoms, dispersed on a nitrogen-doped carbon matrix, and Pt–Fe nanoparticles is shown to exhibit excellent activity and durability in fuel cells.

The widespread adoption of fuel cells requires exhaustive screening for highly active and durable Pt-based catalysts for the oxygen reduction reaction. Now a binary descriptor based on experimental parameters extracted from X-ray absorption spectroscopy is used to predict the catalytic activity and stability of a wide range of Pt-alloy catalysts.

Although pyrene-containing molecules have been studied for their optical properties, the outcome of their incorporation into mechanically interlocked structures remains underexplored. Here, the authors install pyrene units into homo[2]catenanes and investigate the formation of long-lived triplet states, which can be exploited for photocatalysis.

Flavin-dependent halogenases catalyse the challenging regioselective halogenation of aromatic compounds, but display low efficiency. Now, a tryptophan-halogenase with multiple catalytic improvements is obtained by engineering the intermediate transfer tunnel connecting the enzyme´s two active sites.

Cu-based catalysts have dominated CO₂ electroreduction as a result of their unique ability to produce C₂ or C₃ products, while Ni has largely been excluded due to poisoning by intermediate CO. Here, inorganic Ni oxygenate-derived electrocatalysts with polarized Ni^𝛿+ sites can produce multicarbon products, including C₃ to C₆ hydrocarbons.

Catalysis is a crucial strategy for improving the performance of sulfur cathodes in Li–S batteries, yet few strategies have been established to design effective catalysts. Here, by uncovering a volcano-shaped trend between polysulfide adsorption and catalytic rate in transition-metal-doped ZnS, a highly efficient ternary sulfide is developed.

Acidic conditions present a solution to carbonate formation in CO₂ electrolysis but create a selectivity issue through competing H₂ evolution. Here, theoretical methods are used to optimize acidity and select Pd–Cu as a selective electrocatalyst for acidic CO₂ reduction with negligible carbonate crossover and high single-pass carbon efficiency.

The use of ammonia as a nitrogen source in catalytic asymmetric reactions is attractive but represents a difficult exercise. Now, the asymmetric synthesis of N-unprotected α-amino esters from α-diazoesters and ammonia is achieved by cooperative action of copper complexes and chiral hydrogen-bond donors.