Reviews & Analysis

The structure and properties of the electric double layer that forms at the electrode–electrolyte interface is crucial in determining the performance of electrocatalytic reactions. This Perspective puts forward and discusses three major schools of thought on electrolyte effects and electrocatalyst design.

Adsorption on solid surfaces is extremely important for various phenomena and applications. In the 1910s, adsorption and subsequent catalysis was described mainly in terms of diffusion through a fluid film to the interface. Langmuir developed the concept of a monolayer adsorption, which became the cornerstone of modern surface science.

A TIM-barrel metalloenzyme — Art22 — involved in the sugar-moiety modification of the antibiotic aurantinin B (ART B) has been discovered. This enzyme activates 4-keto ART B to ART B through rapid isomerization. Additionally, Art22 slowly converts ART B into inactive products through oxidative cleavage of the 3-keto hexopyranose.

The 1913 study ‘Die Kinetik der Invertinwirkung’, by Michaelis and Menten, marked a pivotal advancement in enzymology by illustrating the application of mechanistic models and quantitative kinetics to biocatalysis. The foundational framework described back then continues to have a strong impact on enzymology, with profound influences that range from undergraduate education to structure–function studies and the format and content of contemporary kinetic databases.

The 2025 RepArtZymes conference featured the latest developments in the design and development of artificial and repurposed enzymes for synthetic and biotechnological applications. These contributions illustrate the impact of this rapidly expanding research area towards addressing key challenges in organic synthesis, medicinal chemistry, polymer chemistry, energy conversion, and environmental remediation.

Tafel slope analysis, first proposed by Julius Tafel in 1905 and supported by the Butler–Volmer equation, is widely used to elucidate electrocatalytic mechanisms and evaluate kinetics. However, some misuses still frequently occur in the literature, calling for rigorous mechanistic investigations at single-crystal electrodes and under well defined mass-transport conditions.

Quantum computing is a promising technology to solve complex challenges that would take classical computers an impractical amount of time. This Perspective discusses the current state of quantum computing and possible applications in enzyme engineering and biocatalysis.

The response of a well-defined Cu pre-catalyst surface to dynamic pulsed electrocatalytic CO₂ reduction conditions is unveiled using a correlated spatially resolved spectro-microscopy approach. The observed structural changes are key to understanding the increased selectivity towards ethanol and ethylene under these conditions.

The evolution of local microenvironments at copper electrodes during the electrochemical CO reduction reaction has long been overlooked. In situ electrochemical surface-enhanced Raman spectroscopy now reveals that the dynamic restructuring of interfacial water resulting from increased local alkalinity enhances the acetate selectivity of this reaction.

The radical S-adenosylmethionine (SAM) enzyme, AbmM, catalyses a replacement of the ring oxygen of a sugar with sulfur. However, how this reaction takes place is unknown. Now, an [Fe₄S₄] cluster is shown to have a dual role in catalysis. It functions in the reductive cleavage of SAM and is the donor of the appended sulfur atom.

Coupled electrocatalytic reactions are of great potential for cost-effective co-production of hydrogen and fine chemicals, yet engineering of catalysts, conditions and cell architectures are still key to delivering this technology at scale. Now, a case study shows the efficient production of 2,5-furandicarboxylic acid enabled by a liquid-cooled kilowatt-scale electrolyser.

The reduction of carbon dioxide (CO₂) to value-added products using sunlight is an attractive technology, especially if multi-carbon products are yielded. Now, the efficient photocatalytic conversion of CO₂ to ethylene is demonstrated by filling the pores of a copper-based metal–organic framework with semiconductor nanoparticles.

The enantioselective aldol reaction of glycinates with aldehydes — a direct entry to an important class of noncanonical amino acids — has so far eluded small-molecule catalysis. Now, mimicking the cofactor of threonine aldolase enzymes, a chiral carbonyl catalyst that is remarkably effective for this reaction has been developed. This asymmetric protocol has been successfully applied to more than a thousand aldehyde substrates.

Changing the catalytic metal centre of a non-haem iron dioxygenase to copper results in an enzyme capable of Lewis acid catalysis of new-to-nature enantioselective Conia-ene reactions.

Precise control of the oxidant — that is, preventing overoxidation — is the missing link in low-temperature methane upgrading. Now, the electro-splitting of carbonate on rutile IrO₂ is shown to cover the surface with on-top oxygen adatoms that act as tethered, single-step hydrogen abstractors. One subset can pull the hydrogen from methane to form a methoxy intermediate, while the neighbouring site can protonate this intermediate to form methanol. Together, this mechanism delivers a room-temperature conversion of methane to methanol with >90% selectivity.

A catalytic system is reported that efficiently converts acetylene impurities into polymer-grade ethylene feedstock by generating hydrogen radicals from water using light as the power source. This system is suggested as a viable sustainable method for ethylene purification.

Understanding the nature of structural evolution of Cu nanocatalysts during CO₂ electroreduction is a long-standing question in catalysis science. Now, operando electron microscopy techniques correlated with X-ray spectroscopy and first-principles modelling demonstrate that the reaction products themselves drive the structural evolution in Cu nanocubes.

The surfaces of solid catalysts undergo dynamic changes, especially in liquid reaction media. Elucidation of mobile Fe species dissolved from a solid NiFe-based electrocatalyst during the oxygen evolution reaction (OER) reveals a solid–molecular mechanism for water oxidation. This mechanism could offer a strategy for enhancing OER activity.

The enantiocontrolled conversion of carbenium ions presents a challenge owing to their instability and high reactivity. Through the combination of a chiral organocatalyst and photocatalyst, the intramolecular enantioselective and enantioconvergent amidation of C(sp³)–H bonds is now demonstrated, affording chiral oxazolidinone products via a transient carbenium ion complex.

Several strategies for the enantioselective synthesis of small cyclic alkanes from achiral building blocks are known, but general and sustainable methods still represent a daunting challenge. Now, the cooperation of asymmetric counterion-directed catalysis with photoredox activation complements metalloorganic and enzymatic methods for the synthesis of chiral cyclopropanes.