Articles in 2024

The development of bimetallic catalysts is often hindered by the heavy workload of the classical trial-and-error method. Now, a distinct mechanism demonstrates that breaking down the net thermochemical reaction into the corresponding electrochemical half-reactions offers a facile approach to design bimetallic catalysts by analysing each putative half-reaction.

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.

The lack of stability of critical raw material-free electrocatalysts during the oxygen evolution reaction in acidic electrolytes lies beneath the use of Ir-based electrocatalysts in polymeric water electrolysis. Here, a strategy to enhance γ-MnO₂ stability in acid is proposed. Theoretical and spectroscopic approaches reveal that increasing the fraction of O atoms in the appropriate position, namely O_pla, prevents Mn dissolution during water electrolysis.

Ethylene oxide is a key platform chemical that is produced industrially from the epoxidation of ethylene on silver catalysts, but the precise mechanism remains elusive. Now, in a joint computational–experimental effort, a phase of the silver catalyst grown on (100) facets that contains square-pyramidal subsurface oxygens and is stabilized by strongly adsorbed ethylene is identified as the active phase, and the mechanism is revealed.

Nanoparticles are often stabilized by capping ligands but the specific role of such ligands during catalytic processes is often ignored. Now, in situ techniques including spatially resolved infrared nanospectroscopy reveal the ligand-assisted formation of a catalytic microenvironment on the surface of silver nanoparticles with nanoscale precision during CO₂ electroreduction.

Unstrained aryl–aryl bonds are among the most inert bonds in organic chemistry. Now the development of a split cross-coupling strategy enables the direct functionalization of such bonds through Rh-catalysed C–C cleavage and cross-coupling with aryl halides, providing a method for biaryl synthesis.

The synthesis of well-defined heterostructure interfaces can be leveraged to design advanced catalysts. Now a catalyst consisting of carbon-supported Janus particles with crystalline Ru and amorphous CrO_x sides is shown to achieve high performance for both alkaline hydrogen oxidation and evolution reactions due to the synergy between both sides.

The electrochemical synthesis of ammonia via the lithium-mediated reduction of N₂ holds great promise to replace the carbon- and energy-intensive Haber–Bosch process. This Review discusses this approach and examines the critical role of the catalytic solid–electrolyte interphase formed on the electrode.

The coenzyme Q biosynthetic pathway has evaded full characterization for decades, in part due to the inherent insolubility of coenzyme Q and the instability of its membrane-associated biosynthetic enzymes. Now, researchers have resurrected an active ancestral coenzyme Q metabolon in vitro that has unveiled valuable insights into previously uncharacterized aspects of coenzyme Q biosynthesis.

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.

Correlating structure and activity is a very important research goal in catalysis. This Editorial reflects on this topic, taking inspiration from examples in the current issue.

In 2018 a descriptor was put forward to correlate the activity of various electrocatalytic reactions on carbon-based single-atom catalysts, but some data the work was based on were later found to be incorrect. This work revisits and amends the original 2018 study while presenting a modified version of the φ descriptor.

Catalytic conjunctive cross-coupling for the generation of densely functionalized sp³-rich scaffolds that are often found in biologically active compounds is underdeveloped. Now, iron-catalysed dicarbofunctionalization of olefins with dialkylzinc and haloalkanes provides access to synthetically challenging C(sp³)-rich molecules.

Mucins are glycosylated proteins with important biological functions such as protection. Although glycopeptidases can cleave them, dedicated hydrolytic enzymes specific for mucins were unknown. Now microbial mucinases are discovered that specifically recognize mucin O-glycan clusters and employ two glutamic acid residues for catalytic cleavage.

The reasons for epistasis, wherein mutations interact non-additively, are often not fully understood. Now it is found that shifting the rate-limiting step from substrate binding to the chemical reaction step during the directed evolution of β-lactamase correlates with epistasis.