Articles

Unlike the more common C–H functionalization, methods for the functionalization of C–C bonds are scarce. Here, Ackermann and co-workers show that an inexpensive manganese catalyst is capable of selectively activating C–C bonds for alkylations, alkenylations, and allylations in water.

Catalysts are dynamic species, whose structure can change over the course of a reaction. Here, structural changes are mapped for cobalt–palladium nanoparticles during CO oxidation, showing a reconstruction to CoO_x on palladium surfaces. Furthermore, the composition-dependent reconstruction can be correlated with the trend in catalytic activity.

One of the major routes for the use of CO₂ in chemical production is the formation of carbonates via cycloaddition of CO₂ to epoxides. This work uses a range of experimental and computational techniques to map out the elusive key intermediates in this process.

Mupirocin is a clinically important antibiotic, but the biosynthesis of its tetrahydropyran moiety—an oxygen heterocycle essential for its bioactivity—has remained elusive. Here, Willis, Crump and co-workers report an enzymatic reaction cascade catalysing this ring formation from a non-activated C–H bond.

The function of putative bacterial vitamin K-dependent carboxylases (VKDCs) has so far been uncertain. Now, Micklefield and co-workers show that a bacterial VKDC orthologue is involved in the biosynthesis of the antibiotic malonomycin, generating an unusual malonic acid moiety that is essential for its biological activity.

The nature of the active sites of molybdenum trioxide and molybdenum carbide, two related catalysts with great potential for hydrodeoxygenation reactions, is still under debate. Now, a comparative operando near-ambient-pressure XPS study during hydrodeoxygenation of anisole reveals important differences between these two materials.

Methanol synthesis from methane is a promising route to valorize this abundant natural gas, but existing thermal processes require harsh reaction conditions. Now, a photocatalytic approach based on TiO₂-supported iron oxide species is described, which affords methanol in high yield and selectivity at ambient conditions.

Catalytic studies on single crystals are very insightful, but it is often difficult to extend their conclusions to an actual catalytic process due to gaps in the experimental conditions. Now, Madix and co-workers report a method to bridge these gaps using the oxidative coupling of methanol on gold as an example.

The reason for the high water-oxidation activity of Ni(Fe)O_xH_y catalysts in alkaline electrolyte is not yet well understood. Now, Chorkendorff and co-workers report that oxygen evolution is limited to the near-surface region by measuring the activity trends of mass-selected NiFe nanoparticles.

The production of higher alcohols is very valuable because of their high volumetric energy density. Now, Sargent, Sinton and co-workers report the design of copper nanoparticles with tailored nanocavities that promote n-propanol formation by the coupling of C2 and C1 intermediates inside the cavity.

Organoboron compounds are versatile intermediates in organic chemistry, and as such the selective introduction of multiple boron-containing groups is of high interest. Here Shi and co-workers report a copper-catalysed method that can selectively introduce two, three or four boronate groups into common starting materials by simply making minor modifications to the reaction conditions.

Manganese carbonyl complexes are promising electrocatalysts for CO₂ reduction, but the intricate mechanisms are difficult to probe. Here, vibrational sum-frequency generation spectroscopy is used to detect the transient catalytic intermediates, providing experimental evidence for the mechanism and demonstrating the utility of the analytical approach for molecular electrocatalytic processes in general.

Platinum group metal- and iron-free catalysts are highly desirable for the oxygen reduction reaction in proton-exchange membrane fuel cells. Now, Wu and co-workers show a carbon catalyst with atomically dispersed single Mn sites as an efficient catalyst with enhanced stability in acidic media.

Improving the stability of proteins for biotechnological applications is challenging. Now, Gillam and co-workers show that the thermal stability and longevity of enzymes can be remarkably enhanced in a single step from sequences of recent ancestors of primitive vertebrates that existed in mild conditions.

Nature’s oxygen-evolving complex of photosystem II is a multinuclear manganese cluster. Whether mononuclear manganese can also efficiently catalyse water oxidation has been a long-standing question. Now, Li and co-workers show that single atoms of manganese can be anchored on nitrogen-doped graphene to catalyse the oxygen evolution reaction. Credit: Water image Frankie Angel / Alamy Stock Photo.

The electrochemical transformation of CO₂ into liquid fuels is a major challenge. Now, Jaramillo, Hahn and co-workers present a Au/Cu catalyst highly active to C₂₊ alcohols at low overpotentials as a result of a tandem mechanism where CO₂ is reduced to CO on Au and further reduced to C₂₊ alcohols on nearby Cu.

Organocatalysed photoredox-mediated atom transfer radical polymerization is a very promising method, although many challenges still lie ahead. Now, Kwon, Gierschner, Kim and co-workers present a computer-aided-design strategy to identify organic photoredox catalysts for this process. The success of the design strategy is demonstrated by polymerizations of methyl methacrylate and styrene.

Single-atom catalysts have proven successful in many catalytic applications. Now, Li, Wu and co-workers show that single-atom catalysts can be prepared directly from bulk metals using an ammonia atmosphere, owing to the formation of volatile metal–ammonia species that are trapped by the nitrogen-rich carbon support.

Although mechanistic understanding can drive new reactivity development, the key bond-forming and -breaking steps in catalytic cycles are often sufficiently fast to elude observation. Here, the authors photochemically produce a key intermediate in Mn-catalysed C–H functionalization, and follow the subsequent steps—spanning processes occurring over seven orders of magnitude in time—using time-resolved infrared spectroscopy.

The precise understanding of the active phase under reaction conditions at the molecular level is crucial for the design of improved catalysts. Now, Strasser, Jones and colleagues correlate the high activity of IrNi@IrO_x core–shell nanoparticles with the amount of lattice vacancies produced by the nickel leaching process that takes place before and during water oxidation, and elucidate the underlying structural-electronic effects.