Volume 1 Issue 1, January 2018

Catalysis is a subject with a surprisingly long and rich history. It seems certain that it has an even brighter future as the challenges of our society require a focus on this discipline more than ever.

Most electrochemical CO₂ reduction research has been confined to fundamental studies that attempt to understand how to overcome low selectivity and energy efficiency for valuable oxygenated products. Now, a modular, scalable system generates multi-carbon oxygenates with a potential solar-to-alcohol efficiency of more than 8%.

Electrophilic substitution of aromatics on zeolites is generally assumed to occur through the Wheland-type intermediate, although direct experimental evidence is lacking. Now, this carbenium ion has been identified as a stable intermediate in the alkylation of benzene with ethanol on an industrial zeolite catalyst.

In nature, a manganese catalyst is used for photosynthetic water oxidation, but efforts to develop artificial manganese-based counterparts have been hampered by the lability of manganese complexes. By using a bulky and hydrophilic ligand, a water-soluble Mn₁₂ complex is found to be a stable and efficient water oxidation electrocatalyst.

Chemical and biological catalysts provide distinct advantages and disadvantages to the synthetic chemist. This Review focuses on efforts to combine chemo- and biocatalysts, outlining the opportunities achievable by this approach and also efforts to overcome any incompatibilities between these different systems.

Bioethanol-based alkylation of benzene is a potentially sustainable route to commodity chemicals, but there is little knowledge of the reaction mechanism. Here, Weckhuysen and co-workers study the zeolite catalysed alkylation of benzene with ethanol, identifying the active alkylating agent and experimentally show the presence of a σ-complex intermediate.

The generation of useful chemicals from CO₂ and renewable energy is an attractive—but challenging—endeavour. This work reports on the long-term operation of commercial electrodes for efficient CO₂ reduction, with subsequent fermentation of the syngas product completing the technical photosynthesis of alcohols.

Hydrogenation is one of the most common catalytic processes on both laboratory and industrial scales, and typically is carried out with a noble metal catalyst. Here, the authors show that alkaline earth metal amides are capable of hydrogenating imines under mild conditions.

During photosynthesis, nature uses an enzyme with a manganese–calcium core for water oxidation. Here, the authors report the synthesis of a stable, water-soluble manganese cluster that acts as a homogeneous water oxidation electrocatalyst, displaying low overpotential and high Faradaic efficiency.

Peroxygenases can selectively functionalize organic compounds, but are sensitive to the co-substrate H₂O₂. Hollmann and co-workers show that water oxidation catalysts can provide a controlled supply of H₂O₂ to the enzyme in the presence of visible light, allowing efficient oxyfunctionalization without stoichiometric reductants.

Atomically dispersed metal catalysts are of increasing importance in many catalytic processes, but clear structural identification is challenging. Here, a general synthesis of metal (nickel, iron and cobalt) single-atom catalysts on nitrogen-doped graphene allows the authors to identify a common structure and furthermore correlate structure with electrocatalytic activity.

Biocatalysis, if selective, offers great potential for the well-controlled release of drugs and other payloads. Here, Minko and co-workers separate enzymes and substrates by loading them onto individual, polymer-coated nanoparticles, and show that a magnetic field switches on the catalytic activity by merging the polymer shells.

Lignocellulose is produced in large amounts as waste but offers the potential of cheap, renewable sources of organic compounds. Here, a process is shown that can derive useful products from all the main components of lignocellulose, giving complete conversion and thus enabling integrated catalyst recycling.