Reviews & Analysis

Phosphorus compounds with unique chirality due to the presence of a P-stereocentre are obtained through stereoselective catalytic cross-coupling of phosphoramidites and aryl halides. Axial-to-central transfer of chirality is shown to provide ready access to various classes of P-chirogenic compounds that are key to catalysis and drug development.

A new class of catalysts based on ternary ruthenium complex hydrides are developed for low-temperature ammonia synthesis. They support a non-dissociative reaction path for dinitrogen reduction, in which lithium or barium cations stabilize the N_xH_y intermediates and the electron- and H-rich [RuH₆]^4– anionic centres facilitate an energetically balanced multi-step reaction for ammonia synthesis.

Liquid fuels produced by electrocatalytic CO₂ reduction are costly to separate from liquid electrolytes in a conventional cell. This Perspective identifies the need for novel cell designs that can directly produce high-concentration and high-purity products and discusses the progress towards this goal using porous solid electrolytes.

The practical implementation of CO₂ electrocatalysis is premised on the availability of captured CO₂—a consideration that is often overlooked. This Perspective presents several concepts for integrating CO₂ capture with electrochemical CO₂ conversion for the enhancement of overall efficiency.

Electrochemical CO₂ reduction is a complex process with many competing products, yet nature has evolved ways to overcome these issues. This Perspective makes connections between the motifs observed in nature and strategies that can be employed in synthetic systems for the advancement of selectivity in CO₂ reduction.

Methanol is a leading candidate for storage of solar-energy-derived renewable electricity as energy-dense liquid fuel, yet there are different approaches to achieving this goal. This Perspective comparatively assesses indirect CO- and direct CO₂-based solar strategies and identifies the conditions under which the former becomes economically viable.

Of the few known catalytic RNAs in biology, all but the ribosome involve reactions with phosphodiester bonds. Now, a ribozyme that catalyses a completely different reaction was discovered in all three domains of life.

Artificial metalloenzymes (ArMs) combine the reaction scope of chemocatalysts with the selectivity of enzymes. This Review discusses the prospects and recent progress in utilizing ArMs in whole cells for applications in diverse areas such as drug therapy and integration with biosynthetic pathways.

Harnessing a clean, affordable and inexhaustible source of energy is an immense scientific challenge. Scientists moved a step closer in 1972 when the first practical device for direct solar power-to-fuel conversion was reported.

The Haber–Bosch process was introduced at the beginning of the twentieth century; however, its mechanism remained controversial for many years. Thus, a comprehensive mechanistic picture was provided in the eighties.

To produce chemicals and fuels from CO₂ and water while storing excess energy from renewable resources will play a big role in sustainability. Three decades ago, we learned that copper possesses the unique ability to break the stable CO₂ bonds and to form C–C bonds, a key step towards higher-value products.

More than 35 years ago, telomerase activity was discovered by Elizabeth H. Blackburn and Carol W. Greider. Today, this enzyme is a promising approach to curing some age-related diseases as well as cancer, but it took time for telomerase to be in the spotlight.

Methods for the direct one-step replacement of a hydrogen atom in a C–H bond by an organic functional group can create enormous possibilities for synthetic applications. On the way to solve this challenge, the discovery of the reaction of organopalladium complexes with olefins opened a new era in catalysis and organic chemistry.

The ability to control the subtle differences in reaction mechanisms and outcomes is an aspiration of many synthetic chemists. Now protein evolution has enabled the control of selectivity for hydroamination reactions catalysed by gold-based artificial metalloenzymes by favouring dual-gold catalysis over monomeric catalysis.

Computational studies have previously explored the effect of cations and hypothesized their vital role in electrocatalysis. Now, experimental evidence shows that without a cation, CO₂ reduction simply does not take place.

Thermocatalytic hydrogenation is used industrially to produce ethylene at a reasonable purity, but at the cost of expensive catalysts, moderate selectivity, and potentially dangerous process conditions. Now, an electrochemical approach based on copper-based electrodes is suggested as a viable sustainable alternative.

Plastics are invaluable materials for modern society, although they result in the generation of large amounts of litter at the end of their life cycle. This Review explores the challenges and opportunities associated with the catalytic transformation of waste plastics, looking at both chemical and biological approaches to transforming such spent materials into a resource.

Electric current is now shown to induce movement of the atoms in electrocatalyst nanoparticles, leading to morphological changes and performance degradation. This electromigration effect needs to be taken into account when designing nanostructured catalysts for electrochemical devices.

Catalysts respond to reactive atmospheres, leading to intrinsically distinct active sites and reaction pathways in response to pressure changes. The degree of pressure gap depends on the nanostructure. Now, the gaps and discrepancies in in-situ and operando studies of CO₂-to-CH₃OH using CuZn catalysts have been rationalized.

Polyamines are a growing class of medically and agriculturally active biomolecules that have traditionally been difficult to source. Now, a bio-based platform for high-level production of diverse polyamines has been realized, showing the versatility of biocatalysis and the utility of conceptualizing metabolism as distinct modules.