Research articles

Achieving plastic deconstruction with high selectivity is crucial for upcycling schemes, but remains challenging. Here, a processive approach for the selective hydrogenolysis of high-density polyethylene into narrow alkane fractions is introduced relying on a Pt/SiO₂ catalyst encapsulated in a mesoporous silica shell.

The development of chiral catalysts is of fundamental importance in asymmetric catalysis. Now, chiral paddle-wheel diruthenium complexes are reported that are stable under oxidizing conditions and effective in asymmetric C–C and C–N bond-forming reactions with turnover numbers of up to 1,880,000.

Improving the kinetics of O₂ reduction on oxide surfaces is critical in many energy and fuel conversion technologies. Now, the authors demonstrate that the acidity of infiltrated surface oxides can serve as a descriptor of the oxygen surface exchange rate on mixed conducting oxides.

Synthetic methods for the green and atom-economical synthesis of thioesters are scarce. Now, a catalytic protocol utilizing a ruthenium pincer complex provides efficient access to thioesters with hydrogen gas as the sole by-product via dehydrogenative coupling of alcohols with thiols.

Single-atom catalysts hold great promise for process optimization by reducing metal utilization. However, their structure–activity properties remain elusive. Here, a combination of operando techniques and density functional theory analysis is used to capture the evolution of single platinum atoms on CeO₂ during CO, C₃H₆ and CH₄ oxidation.

Carbonyl–olefin metathesis reactions are a valuable tool in synthetic chemistry, but there are still some limitations in scope. Now, a catalyst system allows the activation of previously unreactive substrates for such a reaction by aluminium(iii)–ion pairs acting as Lewis acidic superelectrophiles.

Visualizing catalytic processes at the nanoscale is crucial to establish structure–activity relations, but remains very challenging. Here, hydrogen spillover is revealed with a 10 nm spatial resolution during hydrogenation of chloronitrobenzenethiol on a bimetallic Pd/Au catalyst by means of tip-enhanced Raman spectroscopy.

Hydroformylation of alkenes is widely used in industry to synthesize aldehydes, but is less prominent in small laboratories due to safety and equipment issues associated with the CO/H₂ mixture. This is now addressed by generating stoichiometric syngas from two main element compounds, with water as the activator.

CO is a key intermediate in the electro-oxidation of energy carrying fuels which typically acts as a poison. Here, the authors demonstrate that Cu is an efficient CO electro-oxidation catalyst in alkaline electrolyte due to the continuous formation of undercoordinated active Cu adatom sites in the presence of CO and OH.

CRISPR–Cas9 systems have revolutionized the field of genome editing. This work reports rare structures of a Cas9 enzyme (St1Cas9) in its HNH catalytic state, providing mechanistic insights related to DNA recognition and cleavage, and structure-guided engineering is used for expansion of the PAM recognition.

The electrochemical reduction of CO₂ to value-added fuels and feedstocks has recently received a great deal of attention. Here, Cu nanowires that display rich surface steps are reported to sustain C₂H₄ production from CO₂ with a remarkably high Faradaic efficiency for 200 hours.

The fundamental kinetics of the electrocatalytic sulfur reduction reaction, a complex 16-electron conversion process in lithium–sulfur batteries, is a topic that remains largely unexplored. Here, by directly profiling the activation energies in the multi-step reaction, the authors establish how the conversion kinetics differ for each step.

Achieving long-term stability of water oxidation electrocatalysts remains a formidable challenge. Now, an in situ electrochemical reduction strategy to revivify mixed Ni–Fe hydroxide catalysts by reversible phase segregation is presented.

Platinum dissolution and restructuring due to surface oxidation are primary degradation mechanisms of platinum-based electrocatalysts. Now, stark differences are reported in the mechanism for the oxidative extraction of platinum atoms on (111) and (100) single crystals, providing a detailed explanation for the enhanced dissolution on the latter surface.

Site-selective installation of fluorine (¹⁹F) and its radioisotope (¹⁸F) in aromatic molecules can lead to high-value products, but methods for this purpose are not without limitations. Now, using photochemistry, a ¹⁹F- and ¹⁸F- labelling strategy is reported that complements traditional approaches.

Axial chirality is found in many important compounds, such as bioactive molecules and catalytic components. Now palladium and chiral norbornene cooperative catalysis is reported for the construction of atropisomeric biaryls and chiral fluorenols.

The reductive deuteration of unsaturated hydrocarbons is a promising deuterium-labelling strategy, although it requires expensive gaseous D₂ or other stoichiometric reagents. Here, an electrocatalytic palladium membrane reactor is employed to selectively generate C(sp³)–D bonds via reduction of unsaturated compounds using D₂O.

The Mackay crystal is a proposed—but synthetically unachieved—nanocarbon molecule that is anticipated to have many desirable properties. Now, a strategy based on annulative coupling of chlorophenanthrene derivatives is reported, allowing streamlined access to an important substructure.

Isolating the role of water in aqueous reactions where it is directly involved as a reactant is equally important and challenging. Now, by confining water inside an organic liquid matrix, the authors observe the formation of aqueous-rich nanodomains and find that the reactivity of the system varies with their nanostructure.

Computational chemistry has remained largely inaccessible to the experimental chemistry community. Here we report the VIRTUAL CHEMIST, a software suite free for academic use, that enables organic chemists without expertise in computational chemistry to perform virtual screening experiments for asymmetric catalyst discovery and design.