Articles in 2020

The severity of the COVID-19 emergency has forced society to adopt drastic containment measures. In this Editorial we discuss some of their implications for the publishing sector and for our journal.

Electrocatalytic reduction of CO₂ into multicarbon (C₂₊) products is a highly attractive route for CO₂ utilization. Now, a fluorine-modified copper catalyst is shown to achieve current densities of 1.6 A cm⁻² with a C₂₊ Faradaic efficiency of 80% for electrocatalytic CO₂ reduction in a flow cell.

There has been a long-standing debate on whether heterogeneously catalysed Suzuki cross-couplings can occur homogeneously due to metal leaching. Here the authors show that while the palladium from the nanoparticle catalyst is mobile during the reaction, the active sites remain heterogeneous in nature.

Radical S-adenosyl-l-methionine enzymes catalyse challenging chemical reactions, showing potential for biotechnological applications. This Review focuses on enzyme structure–function relationships, providing insights on how these biocatalysts perform different reactions and control the reactive radical species.

Oxidative carbonylation using CO/O₂ is an attractive strategy to construct carbonyl compounds, but the explosive limit of the gas mixture hampers its application. Now, this safety issue is overcome in the aminocarbonylation of alkynes by replacing the external oxidant O₂ by electrochemistry facilitating a mild and safe reaction.

Understanding the surface structure of a catalyst under a reaction environment is challenging, yet necessary. Now, a combination of in situ methods reveals the reversible formation of a surface alloy as the active phase for core–shell Ni–Au nanoparticles during CO₂ hydrogenation, which could not be detected by ex situ methods.

Palladium-catalysed allylic substitution is a widely used method in organic synthesis, although it requires prefunctionalized starting materials or stoichiometric oxidants. Here the authors report a radical route to form π-allylpalladium complexes, and develop a 1,4-aminoalkylation of dienes under redox-neutral conditions.

Reducible metal oxides selectively catalyse the hydrodeoxygenation of C–O bonds in bio-based aromatic molecules, although they show limited performance. Now, using TiO₂ as an example, a method is reported to enhance the activity of the oxide by surface doping with an ultralow loading of Pt.

The structure of core–shell catalysts is often assumed to be conserved over a reaction. Now, an in situ study reveals that the shell of Ni@Au nanoparticles is reversibly converted into a Ni–Au alloy during CO₂ hydrogenation, with important mechanistic implications.

Humankind faces many challenges to continue social and technological development in a sustainable manner. This Comment elaborates how increasing the synthetic capacity of biocatalytic systems can contribute to the United Nations Sustainable Development Goals.

Action for a more sustainable society must be taken — calling for advances in technology. This Insight features artificial biocatalytic systems and functions not found in nature and emphasizes their potential to address major challenges faced by humankind, such as climate change.

The introduction of single abiological catalytic groups enables enzymes to catalyse new-to-nature chemical transformations. Now, this concept is extended to two abiological groups in a single protein scaffold to allow synergistic catalysis in a stereoselective Michael addition reaction.

A shift from sugar-based feedstocks and biomass to the use of atmospheric CO₂ for the bioproduction of fuels and chemicals is desirable. This Review describes how microorganisms can be engineered for CO₂ fixation and industrial valorization of this key molecule.

Synthetic chemical processes often do not operate at sustainable or mild conditions—in contrast with natural complex reaction networks. This Perspective provides a roadmap for bio-inspired integrated catalytic systems for chemical manufacturing, sketching a biologically based future of industrial catalysis.

Artificial photosynthetic technologies could potentially contribute to limiting global warming while providing useful chemicals for society. This Review Article covers photosynthetic semiconductor biohybrids—electrodes/nanomaterials coupled with microorganisms—for light-driven catalytic conversion of CO₂ to fuels and other value-added chemicals.

Spatial organization of biocatalytic cascades can improve their performance. In this Review Article, Itamar Willner and colleagues discuss technologies to artificially confine and localize enzyme cascades, the origin of observed rate enhancements and potential applications of such designed systems.

Nonlinear effects in catalysis have been shown to allow for asymmetric amplification. Here the authors report a particularly intriguing case whereby a catalytic asymmetric reaction gives a significantly higher product e.e. when run with a non-enantiopure catalyst compared to the enantiopure version.

The high reactivity of open-shell alkyl radicals makes their use in asymmetric catalysis challenging. Here the authors report a catalytic enantioselective desymmetrizing reaction of alkyl radicals and diols, forming stereocentres at the reaction site and at sites remote from it.

Platinum nanoparticles have been neglected as a catalyst for acetylene hydrochlorination due to their limited activity. Here, the authors show that nanostructuring to the single-atom level renders platinum on carbonaceous supports a superior catalyst for this important industrial process.