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  • Despite the many recent developments in iron-catalysed cross-couplings, the mechanistic understanding of these reactions is lacking compared to the more studied palladium and nickel variants. Here, the authors find that during iron-catalysed Negishi reactions the diphosphine ligand predominately binds to the zinc—rather than the iron—centre.

    • Antonis M. Messinis
    • Stephen L. J. Luckham
    • Robin B. Bedford
  • Carbon-based single-atom catalysts usually rely on nitrogen co-doping to stabilize the single metal atoms as metal–N4 moieties. Now, Wei, Yao and colleagues make use of operando techniques to show that under alkaline hydrogen evolution reaction conditions the Co–N4 active site undergoes structural distortion to a HO–Co–N2 configuration.

    • Linlin Cao
    • Qiquan Luo
    • Shiqiang Wei
  • Silicon–hydride materials are attractive candidates for the photoreduction of carbon dioxide into fuels, although they have only worked stoichiometrically so far. Now, Ozin and co-workers show how decorating silicon nanosheets with palladium nanoparticles renders the process catalytic.

    • Chenxi Qian
    • Wei Sun
    • Geoffrey A. Ozin
  • Single-atom catalysts are receiving much attention, but insights into their active sites or the differences in reactivity with conventional nanoparticles are still controversial. Now, operando studies on CO oxidation with Ir/MgAl2O4 accompanied by computational investigations reveal important features of this class of catalyst.

    • Yubing Lu
    • Jiamin Wang
    • Ayman M. Karim
  • The use of electrochemistry in asymmetric catalysis can prove challenging, not least due to the difficulty of achieving chemo- and stereoselectivity in combination with very reactive electrochemically generated intermediates. Here, catalytic asymmetric electrosynthesis is reported for the synthesis of 1,4-dicarbonyl compounds with high enantiomeric excess, including compounds with all-carbon quaternary stereocentres. The chiral-at-metal catalyst activates the substrate towards anodic oxidation in addition to controlling the enantioselectivity of the process.

    • Xiaoqiang Huang
    • Qi Zhang
    • Eric Meggers
  • Reusable catalysts based on earth-abundant metals could offer inexpensive and sustainable routes in organic synthesis. Here a nickel catalyst—formed by pyrolysis of a nickel complex on a γ-Al2O3 support—is shown to be highly active for synthesis of primary amines via reductive amination. The catalyst operates with aqueous ammonia and either aldehydes or ketones, tolerating a wide range of functional groups.

    • G. Hahn
    • P. Kunnas
    • R. Kempe
  • The electroreduction of carbon dioxide to formate represents a desirable strategy for the production of fuels and commodity chemicals. Now, guided by density functional theory, Cui and colleagues report CuSn3 alloys that exhibit high activity and selectivity for formate production from CO2 electroreduction at potentials as low as −0.5 V versus RHE.

    • Xueli Zheng
    • Yongfei Ji
    • Yi Cui
  • Copper-based catalysts, especially the so-called oxide-derived copper, are capable of producing multicarbon species from electrochemical CO2 reduction. However, little is known about their active sites despite intensive research efforts. Now, Lum and Ager show that oxide-derived copper catalysts have three distinct product-specific sites for the formation of C2+ chemicals, unlike polycrystalline copper or (111)- and (100)-oriented copper films which show no evidence of product specific sites.

    • Yanwei Lum
    • Joel W. Ager
  • Predicting highly enantioselective ligands for a given asymmetric catalytic reaction is very challenging, but could greatly reduce the need for high-throughput, trial-and-error experimentation. Here, the authors report a freely available, automated tool to identify appropriate chiral ligands for given substrates in asymmetric catalysis.

    • Anthony R. Rosales
    • Jessica Wahlers
    • Per-Ola Norrby
  • Unlike the more common C–H functionalization, methods for the functionalization of C–C bonds are scarce. Here, Ackermann and co-workers show that an inexpensive manganese catalyst is capable of selectively activating C–C bonds for alkylations, alkenylations, and allylations in water.

    • Hui Wang
    • Isaac Choi
    • Lutz Ackermann
  • Catalysts are dynamic species, whose structure can change over the course of a reaction. Here, structural changes are mapped for cobalt–palladium nanoparticles during CO oxidation, showing a reconstruction to CoOx on palladium surfaces. Furthermore, the composition-dependent reconstruction can be correlated with the trend in catalytic activity.

    • Cheng Hao Wu
    • Chang Liu
    • Miquel B. Salmeron
  • The function of putative bacterial vitamin K-dependent carboxylases (VKDCs) has so far been uncertain. Now, Micklefield and co-workers show that a bacterial VKDC orthologue is involved in the biosynthesis of the antibiotic malonomycin, generating an unusual malonic acid moiety that is essential for its biological activity.

    • Brian J. C. Law
    • Ying Zhuo
    • Jason Micklefield
  • The nature of the active sites of molybdenum trioxide and molybdenum carbide, two related catalysts with great potential for hydrodeoxygenation reactions, is still under debate. Now, a comparative operando near-ambient-pressure XPS study during hydrodeoxygenation of anisole reveals important differences between these two materials.

    • Karthick Murugappan
    • Eric M. Anderson
    • Yuriy Román-Leshkov
  • Catalytic studies on single crystals are very insightful, but it is often difficult to extend their conclusions to an actual catalytic process due to gaps in the experimental conditions. Now, Madix and co-workers report a method to bridge these gaps using the oxidative coupling of methanol on gold as an example.

    • Christian Reece
    • Evgeniy A. Redekop
    • Robert. J. Madix
  • The reason for the high water-oxidation activity of Ni(Fe)OxHy catalysts in alkaline electrolyte is not yet well understood. Now, Chorkendorff and co-workers report that oxygen evolution is limited to the near-surface region by measuring the activity trends of mass-selected NiFe nanoparticles.

    • C. Roy
    • B. Sebok
    • I. Chorkendorff