Reviews & Analysis

Nanoscale texture of electrocatalysts, enabled by the tools of nanoscience, is emerging as an important lever for the control of electrochemical reaction pathways.

A crucial malonic acid moiety in the antibiotic malonomycin has been shown to be installed by a bacterial vitamin K-dependent (VKD) carboxylase orthologue.

The biosynthesis of the pharmacophoric tetrahydropyran of the clinically important antibiotic mupirocin remained enigmatic for a long time. Now, research shows that this ring is formed by a unique epoxidation–epoxide-opening cascade starting from a non-activated alkane.

Single-atom catalysts recently attracted considerable research interest for heterogeneous electrocatalysis, including the oxygen reduction reaction. Now, an intriguing two-step approach towards a less explored atomic nitrogen-coordinated manganese with a high loading density has been developed.

The electrochemical reduction of carbon dioxide allows recycling of the greenhouse gas to produce chemicals and fuels. In this Review, Seh and co-workers discuss the progress in operando techniques applied to heterogeneous carbon dioxide electroreduction, highlighting the mechanistic insights that these techniques have provided.

Two-dimensional materials have been in the spotlight since the discovery of graphene, and over time an extensive library of other ultrathin layered structures have emerged. In this Review, Pumera and Chia gather and discuss the features of this class of materials and review their recent applications in electrocatalysis.

Indirect methods are generally adopted to elucidate complicated mechanisms of transition metal catalysis. Now, a way to directly observe transient manganese species and monitor key reaction steps has been established by using time-resolved multiple-probe spectroscopy.

Despite being used as a water-oxidation catalyst in alkaline electrolysis for over a century, the details of how Ni–Fe (oxy)hydroxide catalysts function remains unclear. Now, using a nanoparticle model system, the intrinsic activity and underlying catalytic mechanism is probed.

The mechanism of methanol coupling to methyl formate over single-crystal gold catalysts has been firmly established but barely reconciled with experiments performed under practical conditions. Now, a method to close this gap has been reported, which enables the prediction of the reaction´s selectivity for a broad range of experimental conditions.

The electroreduction of CO represents a promising approach toward artificial hydrocarbon synthesis, but its rate is limited by the sluggish transport of CO in aqueous electrolytes. Recent work shows how the issue can be circumvented by using gas diffusion electrodes.

Development of an earth-abundant and inexpensive copper-based catalyst is desirable for CO₂ hydrogenation. Now, the combined application of a stable copper hydride and a Lewis pair is shown to effect activation of CO₂ as well as heterolysis of H₂, achieving significant turnover numbers.

Heterogeneous photocatalysts are rarely employed in industry for the synthesis of commodity chemicals due to efficiency problems. Now, a photochromic Bi₂WO_6–x/amorphous-BiOCl composite is reported, which features a remarkable activity for the photocatalytic oxidation of toluene into benzaldehyde and benzoic acid.

Artificial metalloenzymes generally consist of a synthetic (organo)metallic catalyst incorporated into a protein. Asymmetric catalysis by such metalloenzymes could result by virtue of the chiral protein environment. Now, redox-sensitive anchoring enables reversible incorporation of an iridium catalyst for transfer hydrogenation.

Typically, catalysts are discovered through trial and error coupled with chemical intuition. Now, an automatic machine-learning framework has been developed that can guide itself to find intermetallic surfaces with desired catalytic properties.

Plasmonic catalysis has recently revolutionized the field of catalysis, promising to achieve improved control over catalytic reactions by targeting specific electronic excitations. In this Review, Linic and co-workers discuss the recent advances in the field, focusing on the underlying physical mechanisms and their application in catalysis, as well as limitations and future perspectives.

The general importance of electrostatic effects on catalysis is well appreciated, but their use in catalyst design is both promising and challenging. This Perspective discusses recent progress and future directions towards computational optimization of biological and chemical catalysis in terms of electric fields and their connections to experimental catalytic systems.

The chemical synthesis of natural products, such as sesquiterpenes, is a daunting task due to their complexity and precise functionalization, and multiple synthetic and purification steps that reduce overall yields are usually required. Now, a highly efficient alternative approach using supramolecular chemistry has been proposed by Tiefenbacher and co-workers.

Metalloprotein activity can be tuned by altering first- and second-sphere interactions with the metal ion or ions. Here, a non-canonical haem axial ligand is introduced into a myoglobin variant, modulating both. The resulting enhancement of cyclopropanation activity illustrates the utility of expanding the suite of available amino acids for biocatalyst engineering.

How the first metabolic network was organized to power a cell remains an enigma. Now, simple iron–sulfur peptides have been used to generate a pH-gradient across a protocell membrane by catalysing hydrogen peroxide reduction. This indicates that short peptides could have fulfilled the role of redox active metalloproteins in early life.

The histidine brace found in certain copper oxidases enables the oxidation of strong C–H bonds in organic substrates. This Perspective highlights and discusses the possible structural and electronic features of this motif and how these features underlie its role in challenging oxidative catalysis.