Volume 3 Issue 2, February 2020

Identifying the rate-determining step (RDS) for oxygen incorporation into mixed ionic and electronic conducting electrodes is very challenging, particularly since the local composition changes during the reaction. Now, a generally applicable method for identifying the RDS is presented, with the example of a Pr_0.1Ce_0.9O_2–x electrode.

Hydrogen peroxide is a powerful oxidizing agent with many applications. Now, a method is presented to generate it from the oxidation of water on a polytetrafluoroethylene-coated glassy carbon electrode with high efficiency.

Electrocatalytic reduction of CO₂ to multicarbon products is useful for producing high-value chemicals and fuels. Here the authors present a strategy that is based on the in situ electrodeposition of copper under CO₂ reduction conditions that preferentially expose and maintain Cu(100) facets, which favour the formation of C₂₊ products.

Late-stage aromatic chlorination of active pharmaceutical ingredients has enormous potential in drug discovery yet still features limited applicability due to issues of functional-group tolerance. Now, dimethyl sulfoxide is reported as catalyst for the chlorination of a diverse family of bioactive molecules in combination with N-chlorosuccinimide.

Identifying rate-determining steps (RDSs) is one of the most challenging aspects of catalysis. This work presents a general framework to identify the RDS of mixed ion and electron transfer reactions, and applies it to the four-electron/two-ion O₂ reduction in solid-oxide fuel cell cathodes, converging on four RDS out of more than 100 possible candidates.

Electrochemical 2e⁻ water oxidation is a promising route for renewable H₂O₂ production but it suffers from low selectivity due to the competing 4e⁻ process. Here the authors demonstrate an interfacial engineering approach where the catalyst is coated with a hydrophobic polymer to confine in situ produced O₂ and promote the 2e⁻ pathway.

In order to use early, non-noble transition metals in homogeneous catalysis, complex ligands are typically needed, offsetting the benefits of inexpensive metals. Here the authors show that a simple manganese complex can be used in the hydrogenation of N-heteroarenes, without the need for additional ligands.

The organocatalysed addition of aldehydes to nitroolefins is an extremely well-studied reaction that almost exclusively provides the syn-configured products. Here a general method to reverse the diastereoselectivity is reported, whereby a tripeptide catalyst consistently provides the anti product with high selectivity.

Despite its potential, catalytic dry reforming of methane has not yet reached practical application due to high thermal energy requirements. Now, a photocatalytic method is introduced based on strontium titanate-supported rhodium nanoparticles that afford syngas production solely under light irradiation.

Amide reduction via hydroboration is challenging, and catalysts often exhibit limited substrate scope. Here the authors report synthesis of a lanthanum cluster as a catalyst for the hydroboration of esters and amides, capable of reducing a wide range of primary, secondary and tertiary amides to amines.

Forming carbon–carbon bonds at the expense of two C–H bonds is difficult, but attractive, as it reduces the number of chemical steps during synthesis by avoiding prefunctionalization. Here such a method is reported, involving an interrupted Pummerer reaction and a photoredox-catalysed coupling.

The photocatalytic decarboxylation of fatty acids affords alkanes under mild conditions, albeit with limited selectivity due to radical-mediated side reactions. Now, a hydrogenated Pt/TiO₂ catalyst is introduced for the selective conversion of C₁₂–C₁₈ fatty acids into C_n–1 alkanes in quantitative yields.