Articles

Plasmas can unlock unconventional reactivity for established catalytic systems, but understanding the resulting mechanistic changes is a complex endeavour. Here in situ characterization techniques allow us to rationalize the promotional role of non-thermal plasma on the catalytic hydrogenation of CO₂ to methanol on Cu–Zn systems.

Predicting the function of enzymes remains difficult and current computational methods require improvement. Now EnzymeCAGE, a geometric deep learning model, has been developed to more accurately predict the functions of uncharacterized enzymes and reconstruct biosynthetic pathways.

Single iron atoms on nitrogen-doped carbon catalysts are a promising alternative to platinum for the oxygen reduction reaction on fuel cell cathodes, but commonly suffer from low stability. Here an in situ chemical vapour deposition synthetic approach is presented, enabling high iron active site dispersion and reducing surface porosity, which mitigates demetallation and carbon corrosion, ensuring high activity and stability.

The enantioselective construction of α-diheteroatomic carboxylic acids has long been a synthetic hurdle. Now, a thia-Rh-carbene platform enables O–H or N–H insertions, delivering this rare chiral motif for applications in peptide chemistry and drug development.

The catalytic asymmetric Michael addition to α,β-unsaturated carbonyl compounds is one of the most valuable methods for the construction of β-carbon chiral centres. Now the authors report a Pd-catalysed asymmetric anti-Michael-type addition of carboranes to α,β-unsaturated carbonyl compounds.

Light-driven enzymatic catalysis has enabled important abiological transformations in vitro. Now a cellular ene-reductase photoenzyme is integrated with a de novo-designed olefin biosynthetic pathway for photoinduced hydroalkylation, hydroamination and hydrosulfonylation reactions within cells.

The success of photocatalytic coupling of CH₄ has been limited by the low solar absorption of wide-bandgap semiconductors and the uncontrolled oxidation caused by radical oxygen species. Here a Pd/Co₃O₄ heterojunction derived from a metal–organic framework demonstrates the selective conversion of CH₄ to C₂H₆ by less reactive oxygen species under full-solar-spectrum irradiation.

Nickel-catalysed cross-coupling reactions generally use Ni(II) or Ni(0) precatalysts. Here the authors report thermally stable dinuclear Ni(I) complexes with commercial isocyanide ligands for the efficient catalysis in Kumada, Suzuki–Miyaura and Buchwald–Hartwig cross-coupling reactions.

Earth-abundant cobalt-based catalysts have shown promise to replace iridium as anode catalysts in proton-exchange-membrane water electrolysers, but unfortunately they exhibit high degradation rates. Now, a lanthanum and calcium co-modification of Co₃O₄ is presented, in which lanthanum tunes the water–surface interactions to suppress cobalt dissolution and improve stability, while calcium leaching creates coordinatively unsaturated cobalt sites, leading to enhanced activity.

Electrocatalysis is a powerful tool in organic synthesis, but asymmetric strategies are still less developed. Now a cobalt/pyridoxal electrocatalytic system facilitates electrochemical single-electron transfer and asymmetric induction for the enantioselective generation of α-quaternary amino esters.

Titanosilicates in combination with H₂O₂ catalyse the ammoxidation of cyclohexanone to cyclohexanone oxime, a key Nylon precursor. Integrating a step for the in situ synthesis of H₂O₂ can lead to important efficiency gains but remains challenging. Here the authors report low-loaded subnanometric Pd clusters on titanium mordenite as an efficient catalyst for this transformation.

Monitoring charge carrier dynamics and photocatalytic reaction rates in individual photocatalyst particles is a challenging task that can help us to understand structure–reactivity relationships. Here single-molecule fluorescence imaging is coupled with femtosecond interferometric scattering microscopy to investigate these properties in 2D InSe flakes.

The stability of PEM water electrolysers is severely affected by the purity of the water employed. Here a cobalt-doped RuO₂ catalyst is developed to operate with water treated with reverse osmosis, which contains a significant amount of residual ions, achieving a degradation rate of only 10 μV h⁻¹ after 2,000 h of continuous operation at 1 A cm⁻².

Insights from surface science studies on model catalysts very often do not translate to practical catalytic systems due to the so-called pressure and materials gaps. Now, a combination of in situ microscopy, spectroscopy and computational modelling is used to bridge the knowledge from surface science and powder catalysts for FeO–Pt during CO oxidation.

Proton-exchange membrane water electrolysers rely on iridium to catalyse their anodic reaction, and while ruthenium is a less costly alternative due to its similar activity, it is not as stable. Now, a hierarchical machine-learning catalyst discovery workflow, termed mixed acceleration, is put forward to predict catalyst synthesis, activity and stability, and identify promising RuO_x-based water oxidation catalysts.

Radical ligand transfer is a common reactive pathway in 3d transition metals. Here the authors describe it for 5d transition metals in dinuclear gold complexes, for the formal addition of unactivated C(sp³)–Cl bond in gem-dichloroalkanes and Freon-22 to different kinds of alkenes.

Selective oxidation of biomass-derived precursors has been reported but requires elevated temperatures and pressures of O₂ and strongly alkaline conditions. This study develops an antenna–reactor plasmonic photocatalyst (RuPt on TiN) for the selective conversion of HMF to FDCA using near-infrared irradiation in the absence of base.

Photoexcited nitroarenes are traditionally consumed as reactive intermediates in transformations. Now, it is shown that simple and cheap nitroarenes can be used as energy transfer photocatalysts in reactions such as E-to-Z alkene isomerization and [2 + 2] intramolecular cycloadditions.

Electrocatalytic CO₂ reduction is typically studied at laboratory scale under ambient conditions; however, temperature and pressure may have a profound impact on the mechanism of this reaction and on its relevance to industrial applications. This study uses a custom temperature- and pressure-adjustable cell to reveal a chain growth mechanism emerging on copper electrodes at elevated temperatures and pressures.

Catalytic asymmetric all-carbon-based inverse-electron-demand Diels–Alder reactions are challenging. Now, transition metal catalysts enable formal inverse-electron-demand [4+2] cycloaddition reactions of Morita–Baylis–Hillman carbonates with 1,3-unsaturated compounds to afford chiral cyclohexene derivatives.