Articles

Aminated heteroaromatics are usually synthesized from heteroaromatic substrates. Now, a general photochemical approach that exploits non-aromatic N-heterocyclic ketones as starting materials for the coupling with amines under desaturative catalysis is reported as an alternative.

Synthetic methylotrophic organisms provide potential for valorization of greenhouse gas-derived methanol. Here an Escherichia coli strain is generated that reaches a similar growth rate on methanol to many natural methylotrophs and is capable of producing chemicals from this carbon source.

The tunable design of molecular catalysts presents opportunities for the control of product selectivity in CO₂ reduction, yet to date, complexes capable of producing multicarbon products have been elusive. Here, a Br-bridged dinuclear Cu(I) complex that turns over C₃H₇OH is reported.

Electrocatalysts are often dynamic and their surface structure changes under working conditions. Now the dynamic evolution of MoS₂ edges is monitored with nanometre-resolution via electrochemical tip-enhanced Raman spectroscopy during the hydrogen evolution reaction.

The development of superior and cost-effective catalysts for the oxygen reduction and evolution reactions is pivotal for the future hydrogen economy. Now a series of Ru-modified Li₂MnO₃ catalysts have been designed to optimize the electronic structure and achieve a high performance in both oxygen reduction and evolution reactions, as demonstrated in practical anion exchange membrane fuel cell and water electrolyser tests.

Photoelectrocatalysis offers the potential to reduce energy demand and provide different selectivity profiles compared with electrocatalytic analogues, but current systems have shown limited rates. Here, recent advances in light concentration and gas diffusion electrodes are integrated into a photoelectrochemical system for coupled glycerol oxidation and CO₂/H₂O reduction with photocurrent densities above 100 mA cm⁻².

Oxide-derived copper is well-known as a CO₂ reduction electrocatalyst, yet the mechanism of its formation and the structure of the active phase remain unclear. Here the reduction of oxide-derived copper is modelled using large-scale molecular dynamics with a neural network potential, providing important insights into the removal of trapped oxygen under operating conditions.

Photoelectrocatalytic nitrate reduction offers an opportunity for a lower carbon route to ammonia production but has not been realized due to poor efficiency. Here an efficient modified lead halide perovskite photocathode is coupled to glycerol oxidation anode resulting in a bias-free photocurrent density greater than 20 mA cm⁻².

Polar and steric effects usually dictate the regioselectivity in homolytic aromatic substitution. Now a method for direct ortho-selective C–H amination of aromatics with diverse side chains as directing groups is disclosed, by which the iron catalyst coordinates both the substrate and the aminyl radical.

The semihydrogenation of acetylene is an important industrial reaction generally targeted with alloy catalysts and more recently with single-atom catalysts. Here, the authors report a MOF-supported Pd₁–Au₁ dimeric system that, by merging such approaches, results in high performance levels under simulated front-end industrial conditions.

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.

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.

[Cu(phen)(binap)]⁺ features a relatively high photocatalytic activity, but its low photostability hinders its use in organic chemistry. Now immobilization of this motif on a metal–organic framework matrix enhances its stability and excited-state lifetime, enabling the promotion of [2+2] cycloadditions of styrenes with a variety of olefins, including electron-deficient alkenes.

Electrochemical cross-electrophile coupling with alkyl halides for the construction of C(sp³)–C(sp³) bonds is generally limited to activated alkyl halides. Now this approach is extended to coupling of unactivated alkyl halides using a nickel catalyst under mild conditions.