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Gaining complete understanding of complex reaction networks is pivotal for process optimization, yet it is a very challenging endeavour. Here, Javier Pérez-Ramírez, Patrick Hemberger, Guido Zichittella and colleagues employ operando photoelectron photoion coincidence spectroscopy to monitor the mechanistic intricacies of the methanol and methyl chloride conversions to hydrocarbons on zeolite catalysts.
General catalytic methods for free radical-mediated asymmetric transformations have long eluded synthetic organic chemists. Now, NAD(P)H-dependent ketoreductases are repurposed and engineered as highly efficient photoenzymes to catalyse asymmetric radical C–C couplings.
Elucidating the reaction mechanism of a catalytic process is very challenging. Now, advanced solid-state nuclear magnetic resonance experiments demonstrate the importance of oxygenates to regulate the conversion of synthesis gas over an oxide–zeolite-based bifunctional catalyst material.
Engineering enzymes to perform new-to-nature reactions can address long-standing challenges in synthetic chemistry. Now a ketoreductase has been evolved to undergo a photoinduced single-electron-transfer pathway, thereby achieving an enantioselective Giese-type radical conjugate addition that yields α-chiral esters.
Syngas conversion to hydrocarbons on oxide–zeolite bifunctional catalysts is a promising process, yet a complete mechanistic understanding is still lacking. Now the reaction network has been comprehensively evaluated on ZnAlOx/H-ZSM-5 using a combination of NMR- and gas chromatography-based techniques.
The conversions of methanol or methyl chloride over zeolite catalysts are promising processes to produce valuable hydrocarbons, but their mechanisms are still not fully understood. Now these are evaluated using operando photoelectron photoion coincidence spectroscopy, which enables the direct observation of elusive intermediates such as methyl radicals or ketene.
The deployment of fuel cells demands more efficient electrode–electrolyte interfaces to catalyse the oxygen reduction reaction (ORR). A kinetic ORR descriptor is put forward, which is related to the rate of the *O ↔ *OH transition and includes electrolyte effects via the role of non-specifically adsorbed anions.
Alkali metal cations influence electrocatalytic reactions, but their specific role remains elusive. Now, methyl4N+ is established as a vibrational probe for surface-enhanced infrared absorption spectroscopy, revealing that alkali metal cations specifically adsorb on Au during CO2 electroreduction and that their surface coverage depends on their free energy of hydration.
Conversion of CO2 to fuels or chemicals via artificial photosynthesis usually requires the assistance of organic additives or electricity. Now, a biohybrid system is reported consisting of a photocatalyst sheet and bacteria producing acetate and O2 from CO2 and H2O using sunlight as the sole energy input.
Allylic amination of unactivated alkenes with aliphatic amines is a long-standing synthetic challenge in organic chemistry. This is now accomplished in an oxidant-free, site-selective process by using a combination of a photocatalyst and cobalt complex for the coupling of olefins and alkyl amines with hydrogen evolution.