Search

Metal–ligand cooperative catalysis involves both the metal and the ligand moieties present in a complex interacting with substrates. Cooperative catalysis is central to the mechanisms of hydrogenases, lactate racemase and alcohol dehydrogenase. This Perspective describes these enzymes, as well as the small-molecule mimics inspired by these elaborate natural catalysts.

A dual-cofactor artificial metalloenzyme is developed, incorporating a biotinylated nickel complex and a Strep-tagged peptide catalyst in adjacent streptavidin-binding sites. This synergistic artificial metalloenzyme achieves enantiodivergent Michael addition reactions with tunable stereochemistry and high turnover numbers across diverse ketone and enal substrates.

Direct synthesis of aryl amines from nitroarenes avoids the waste and potential functional group incompatibility of first reducing to anilines. Here, the authors report an iron catalysed reductive coupling of nitroarenes with alkyl halides to form a wide range of (hetero)aromatic amines.

While methods for arylation of amines are well established, alkylation is a less well-developed process. Here, Hu and co-workers report amine alkylation using redox-active esters, using a combination of photoredox catalysis to generate the active electrophile and copper catalysis for the cross-coupling.

Detailed knowledge about its catalytic process is important for exploiting [Fe]-hydrogenase—an enzyme that cleaves and produces H₂—for technological purposes. This study presents an atomic-resolution crystal structure of a substrate-bound closed active form of the enzyme and a precise catalytic cycle.

Metal selenides have been reported as promising oxygen-evolution catalysts but their active forms are yet to be elucidated. Here, the authors show that metal selenides are unstable under oxygen-evolution conditions and that in situgenerated metal oxides/hydroxides are responsible for their high activity.

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.

Photoelectrochemical cells have been widely used for the production of solar fuels, but have seen limited applications in organic synthesis. Here the authors demonstrate photoelectrocatalytic C–H amination of aromatics, using haematite as the photoanode.

An optimized Co–Ni alloy catalyst encapsulated with Sm₂O₃-doped CeO₂ shows both high activity and stability for high-temperature CO₂-to-CO conversion, overcoming the limitations of such catalysts typically used in industrial applications.

The search for efficient catalysts for the oxygen evolution reaction is ongoing. Here, the authors show that liquid exfoliation of layered double hydroxides yields single-layer nanosheets with enhanced catalytic activity, attributed to the more numerous active sites and increased electronic conductivity.

Natural hydrogenases exclusively utilize Ni and/or Fe to activate or produce hydrogen. Now, a catalytically active [Mn]-hydrogenase has been prepared by incorporating a synthetic Mn complex into the apoenzyme of [Fe]-Hydrogenase. The semi-synthetic [Mn]-hydrogenase shows higher activity than the corresponding Fe analogue.

[Fe]-hydrogenase has an iron-guanylylpyridinol cofactor and catalyses the reversible hydrogenation of a methenyl-tetrahydromethanopterin. Now, [Fe]-hydrogenase has been reconstituted using synthetic cofactor mimics. The enzyme containing a mimic with a 2-hydroxy-pyridine group was active, whereas one containing a 2-methoxy-pyridine group was inactive. This result, together with DFT computations, supports a catalytic mechanism involving the deprotonated pyridinol hydroxy group as a proton acceptor.

Scrutinizing the metal nitride/oxide interface reveals the chemical origin of the enhanced oxygen reduction activity of metal nitrides.

Hydroxide exchange membrane fuel cells are promising devices for energy conversion. Now, a porous nitrogen-doped carbon-supported PtRu catalyst for the hydrogen oxidation reaction is presented, consisting of Pt single atoms and PtRu nanoparticles that work synergistically. The catalyst enables a fuel cell that exceeds the US Department of Energy 2022 performance target.

Direct conversion of esters to amides, while attractive, is often limited to activated esters or highly nucleophilic amines. Here the authors report a nickel-catalysed reductive coupling between unactivated esters and nitroarenes, giving a direct route to aromatic amides.

Photoelectrochemical water splitting may be used to produce hydrogen using abundant solar energy. Here, the authors fabricate layered films of amorphous molybdenum sulphide on copper(I) oxide and demonstrate the catalytic activity and enhanced stability of these devices made from earth-abundant materials.

Oxygen evolution reaction (OER) catalysts often comprise multiple metal ions in various configurations, hampering mechanistic understanding of how catalysis proceeds. Now, researchers prepare a series of double-atom OER catalysts based on Ni, Fe and Co, which act as molecular-like models and are more amenable to mechanistic study.

Acidic media provide an opportunity to alleviate carbonate formation in electrocatalytic CO₂ reduction but increase competition from H₂ evolution. This study demonstrates that alkali cations in acidic media suppress H₂ evolution leading to high Faradaic efficiency for carbon-based products and models the physical effects that lead to this result.

Hydroxide exchange membrane fuel cells are promising as an energy conversion technology, but require platinum group metal electrocatalysts for their application. A Ni-based hydrogen oxidation reaction catalyst is now shown to exhibit unprecedented electrochemical performance.

Methods for producing organic molecules rich in sp³-hybridized carbon centres can be particularly useful for drug development. Now, it has been shown that the enantioselective cross-coupling of non-activated alkyl halides with alkenyl boronates enables the synthesis of chiral alkyl boronates. The reaction proceeds via nickel hydride insertion into an internal alkene followed by nickel-catalysed alkyl–alkyl cross-coupling.

While solar-to-fuel catalysis requires the careful transfer of electrons, there are still challenges understanding how electron spin contributes to reactivity. Here, authors employ chiral fused thiadiazole-helicenes to control spin polarization in oxygen evolution electrocatalysts.

Operando monitoring of mass transport kinetics and lithium dendrite growth in lithium metal batteries and parametrization of the batteries’ electrochemistry and safety have been achieved using optical fiber sensors.