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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.
Electrocatalytic mechanisms may underpin the function of what appear to be thermocatalytic reactions. Now, a probe molecule-based approach directly measures the extent of electrochemical polarization in operating catalysts.
Using a single ruthenium catalyst, site-selective C–H functionalization methods are developed for the installation of silylmethyl synthetic handles at either ortho or meta positions on diverse arenes, enabling a wide range of downstream transformations. Mechanistic studies highlight that biscyclometallated ruthenium(II) species are key to this reactivity, offering insight for future developments.
The catalytic enantioselective formation of alkyl−alkyl bonds from simple feedstock chemicals remains a formidable challenge in organic synthesis. Now, an enantioconvergent approach that couples styrenyl aziridines with unactivated olefins using a chiral nickel catalyst and visible light has been developed.
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.
Interfacial polarization influences catalytic reactions occurring at solid–liquid interfaces, but its measurement was previously limited to conductive materials. Now redox-active molecules enable electrochemical potential measurements of metal catalysts, even on insulating supports.