Research articles

Understanding how copper nanoparticles evolve under electrochemical conditions is crucial for the development of selective CO₂ reduction electrocatalysts. Here the authors prepare well-defined nanocrystals and use advanced operando imaging and spectroscopic techniques to reveal the Cu–CO species-driven dynamic evolution of Cu electrodes.

There are issues hampering the wider adoption of atom transfer radical addition (ATRA) of aroyl chlorides to access β-chloroacyl derivatives via photoredox catalysis. Now, Mandal et al. report the regioselective chlorocarbonylation of alkenes and alkynes via visible-light-mediated ATRA of aroyl chlorides catalysed by a heteroleptic Cu(I) complex.

Remote C–H bond formation via photoenzymatic hydrogen atom transfer has enabled the precise installation of remote stereocentres but is still in its infancy. Here, the authors report the photoenzymatic stereoablative enantioconvergence of γ-chiral oximes using repurposed flavin-dependent ene-reductases.

General methods to access stereogenic centres of different heteroatoms are limited. Now the nickel-catalysed enantioselective construction of carbon, boron and germanium-centred chiral spirocyclic frameworks via a hetero [2+2+2] cycloaddition of a bis-alkyne with a nitrile is presented.

Solution-based methods exist to upcycle waste polyolefins, although these resort to the use of co-reactants and require non-negligible energy inputs. Here the authors show how a solar thermal catalytic system based on copper particles encapsulated within a 2D Si material can strongly alleviate such issues.

Promoters are able to modulate the performance of catalysts for a given process, but this can be done through various mechanisms. Here the role of Mn as a promoter on Fe-based catalysts for CO₂ hydrogenation to olefins is comprehensively investigated via spectroscopic and kinetic analyses. The promoter induces a restructuring of the catalyst surface, balancing the strength of the adsorption of reactants and intermediates.

Single-atom catalysts commonly present a random distribution of the active metal centres. Now a series of Mg-rich intermetallic compounds is introduced to enable ordered dispersed active metals. Furthermore, a cascade process is demonstrated on Mg₂₉Pd_1.3Rh_2.7, where Pd sites catalyse the semihydrogenation of phenylacetylene with subsequent hydroformylation on Rh sites.

H₂O₂ is a commodity chemical produced in industry via the anthraquinone process from H₂ and O₂. Now a heterogeneous catalysis approach is presented in which H₂O₂ is synthesized from H₂O and O₂ on defective SnSe nanosheets at ambient conditions.

Electrocatalytic CO₂ reduction has largely been limited to C₁ and C₂ products, especially at high current densities. Here, a Faradaic efficiency of 67% is reported for C₃₊ products from CO₂ at 1.1 A cm⁻² via a formaldehyde condensation mechanism on a phosphorus-rich copper catalyst.

Synthetic methods to generate tertiary nitroalkanes are scarce. Now the cobalt-catalysed synthesis of tertiary nitro-containing compounds under mild conditions from easily available olefins is enabled by a nitro-transfer reagent containing an anomeric amide.

NiFe-based catalysts are promising for water oxidation in alkaline electrolytes, but their dynamic structure under operation hinders the establishment of design principles for improved catalytic performance. Now a water oxidation mechanism on mixed NiFe hydroxide catalysts is proposed that involves dissolved FeO₄²⁻ species acting as co-catalysts.

Transformations from carbenes to olefins have generally been realized with transition metal-catalysed enantioselective methods or artificial metalloenzymes. Here the authors apply asymmetric counteranion-directed photoredox organocatalysis for the highly enantioselective cyclopropanation of styrenes and aliphatic dienes.

The electrochemical behaviour observed during water reduction and oxidation is considerably more complex under mild pH than under strongly acidic or alkaline conditions. This Analysis explains the origins of this behaviour and presents its implications for aqueous electrocatalysis.

Enantiocontrolled transformation of carbenium ions is challenging due to their instability and high reactivity. Now, combining a chiral organocatalyst with a photocatalyst enables enantioselective intramolecular amidation of C(sp³)–H bonds to afford chiral oxazolidine products via a transient carbenium ion complex.

Engineered polyketide synthases (PKSs) have great potential as biocatalysts for the synthesis of chemically challenging molecules. Here the authors show a retrobiosynthesis approach to design and construct PKSs to produce a series of valerolactams for biopolymer production.

Supported single atoms are promising catalysts for alkane dehydrogenation, although tuning their reactivity via active site modulation remains a challenge. Here the authors introduce an Ir₁–Cu₁ dual-atom catalyst for n-butane dehydrogenation that outperforms the corresponding Ir₁ single-atom system.

Propane dehydrogenation is an important reaction for the production of propylene, although effective catalysts are generally constructed from precious metals. Here, the authors report a high-performing earth-abundant alternative system for this reaction based on a particular form of cobalt on siliceous zeolites.

Single-atom Fe–N–C catalysts are the most promising alternative to Pt-group metal catalysts for the cathodic oxygen reduction reaction in fuel cells, but while the chemical environment of their active centres is well understood, their electronic structure remains elusive. Now, using molecular model catalysts, a high-spin trivalent FeN₄ site with an axial hydroxyl ligand is identified as the active site in Fe–N–C catalysts.

Despite the importance of chiral macrocycles, their synthesis has lagged behind those of normal and medium-sized rings. Now a bio-inspired catalytic metallic dipole relay strategy enables access to the synthesis of axially chiral 14-, 15- and 20-membered macrocyclic products.

Nitric oxide is an environmental pollutant that is typically remediated by selective catalytic reduction at elevated temperatures. Here an electrochemical oxidation pathway is reported at near-ambient conditions, producing a concentrated stream of nitric acid as a valuable product from waste nitric oxide streams.