Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain
the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in
Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles
and JavaScript.
The overall water splitting performance of semiconductor photocatalysts is often limited by recombination reactions occurring at the surface of metallic co-catalysts. Here, the authors demonstrate how the controlled deposition of aluminium oxide species on a Rh co-catalyst can strongly inhibit this phenomenon and enhance the performance of GaN–ZnO photocatalyst.
Insights on the mechanistic differences between artificial metalloenzymes (ArMs) with non-native metal centres and the free cofactor or natural enzymes are scarce. Now, a detailed mechanistic analysis of a cyclopropanation reaction catalysed by such an ArM is provided, revealing intriguing differences to the natural system.
Renilla luciferase is a popular bioluminescent enzyme, but the molecular details of its mechanism of action on luciferins such as coelenterazine remained elusive. Now, protein crystal structures and biochemical analyses provide an atomistic description of its catalytic mechanism.
Biocatalytic methods to access thioesters, such as acyl-coenzyme A, from carboxylic acids are underdeveloped. Now, it is shown that the adenylation domain of a carboxylic acid reductase enzyme can be exploited as a promiscuous thioester synthetase and combination with acyltransferases facilitates the synthesis of amides and peptide labelling.
Hydrogenolysis of unactivated C(aryl)–C(alkyl) bonds is a challenging task even in the presence of metal catalysts. Now, an approach using a boron catalyst is described that facilitates the hydrogenolysis of alkylarenes under mild conditions, and its utility is demonstrated by degrading polystyrene waste into benzene and phenylalkanes.
Simultaneous stereochemical control of two vicinal C(sp3) stereocentres from two reaction partners is challenging. Now, this is achieved in a nickel-catalysed enantio- and diastereoselective cross-coupling reaction of internal alkenes with racemic alkyl bromides.
Electrocatalytic hydrogenations of organics allow water to be used as the proton source but are limited by low substrate solubility in aqueous media or by low performance in organic electrolytes. Now, a Pickering emulsion system for electrocatalytic hydrogenation is presented to overcome those issues, where the hydrogenation reaction occurs at the interface between the aqueous and organic phases.
Operando investigation of the CO2 reduction mechanism at gas diffusion electrodes is a challenging task. Here proton-transfer-reaction time-of-flight mass spectrometry has been deployed to analyse the intermediates and products at copper electrodes in real time.
Activation of inert chemical bonds employing classical photocatalysts usually involves an outer-sphere single electron transfer mechanism. Now, an alternative inner-sphere single electron transfer pathway for the homolytic cleavage of strong C–Cl bonds using gold catalysts is reported.
The Birch reduction is one of the methods of choice to perform the hydrogenation of arenes, although it requires the handling of pyrophoric substances and ammonia at cryogenic temperatures. Here a photocatalytic approach based on boron carbonitride introduces the possibility to hydrogenate (hetero)arenes under mild conditions in water.
Despite great progress in electrocatalytic CO2 reduction on Cu-based materials, the selectivity for methanol has remained elusive in contrast to thermocatalytic routes. Here, using Cu2NCN with polarized Cu atoms as the cathode, selectivity of up to 70% for methanol is achieved by favouring cleavage of Cu–O over O–C in the crucial Cu–*O–CH3 intermediate.
While the promise of low metal utilization has brought single-atom catalysts (SACs) into the spotlight, intrinsic limits in reactivity still restrict their application to a small set of reactions. Here, the authors expand the repertoire of SAC transformations with a nitrogen-doped, carbon-supported, Ru single-atom catalyst that exploits the effect of peripheral N species to promote propane dehydrogenation.
Controlling selectivity during direct unsymmetrical diamination of double bonds is challenging. Now, ambiphilic iminyl and electrophilic amidyl radicals are generated from oxime ester-based bifunctional precursors, enabling the regio- and diastereoselective unsymmetrical diamination of arenes and alkenes.
Iridium catalysis can be used to achieve the challenging Z-retentive asymmetric allylic substitution reaction by trapping thermodynamically less stable anti-π-allyliridium intermediates. Now the isolation and characterization of these complexes is reported, providing hitherto elusive detailed mechanistic insights into this reaction.
The mode of action of the biological Dnd antiphage defence system to cleave foreign DNA was not known. Now the activities of Dnd protein complexes are revealed, and a mechanism to discriminate between self-DNA and invading DNA is proposed.
Carbonyl catalysis is mainly limited to strongly activated primary amines. Now, a chiral bifunctional pyridoxal organocatalyst is developed that enables the activation of the inert α C(sp3)–H bond of NH2-unprotected benzylamines affording chiral β-aminoalcohols with high diastereo- and enantioselectivities.
Copper is unique among CO2 electrocatalysts owing to its ability to produce multicarbon products at high rates; however, achieving selectivity for specific products remains challenging. Here, Cu surfaces decorated with alkaline earth metal oxides are found to strongly favour alcohols over hydrocarbons.
The hydrogenation of CO2 into more valuable hydrocarbons is potentially attractive in the context of greenhouse gas removal schemes, although the efficiency of such processes is still limited. Now, a GaZrOx oxide catalyst working in combination with an H-SSZ-13 zeolite enables the highly efficient hydrogenation of CO2 to propane with minimal by-product production.