Search

Microbial cells have emerged as a versatile platform for the synthesis of metal nanoparticles, but their application to produce single-atom catalysts (SACs) has been rarely studied. Here, the authors develop a facile method for the ambient synthesis of SACs with a high loading by in situ reduction of metal ions on the cells overexpressing a catalytically active enzyme, producing chemo-bio bifunctional catalysts (SAC@cell).

Engineering metal-ion vacancy in dynamically reconstructed catalysts under operating conditions is attractive for practical utilization. Here, the authors report a Sr-mediated reconstruction method to dynamically fabricate Co-vacancy-enriched Sr-CoOOH for water electrolysis.

The development of a Late-stage functionalization strategy to introduce functionalizable groups provides a toolbox for future drug discovery. Herein, the authors report a synthetic strategy for the N-methyl selective alkenylation and alkynylation of aliphatic tertiary amines using organophotoredox catalysis, and its application to the late-stage functionalization of marketed drugs.

The reverse water–gas shift reaction is crucial for CO₂ conversion using renewable hydrogen, but simultaneously achieving high activity, selectivity, and stability in catalysts remains a challenge. Here, the authors introduce a near-surface “quasi-hyperbaric” ammonia strategy that integrates atmospheric-pressure processing with in situ ammonia decomposition to synthesize a high-energy Mo₂N-based catalyst capable of overcoming these trade-offs.

Atomic catalytic pairs enable multistep transformations, yet the roles of spatial arrangement and coordination symmetry in homonuclear pairs remain unclear. Here, the authors construct atomically dispersed homonuclear Pt₁–Pt₁ pairs with asymmetric Pt₁C₃–Pt₁O₁C₃ coordination on reduced graphene oxide, enabling efficient transfer hydrogenation of azobenzene.

Valorizing plastic waste remains a major challenge due to its severe environmental impact. Here, the authors report a CuCo/CoOₓ catalyst constructed via stepwise hydrogen spillover, enabling near-quantitative conversion of waste polyethylene terephthalate to p-xylene.

This work develops an atomic-level coordination engineering strategy that strengthens key intermediate adsorption to promote C–C coupling, enabling highly selective photocatalytic CO₂ conversion to ethylene.

Metal–ligand synergistic catalysis remains underexplored in single-atom systems. Here, inspired by homogeneous pincer complexes, the authors construct Pd(II)–N₄ sites on carbon nitride, enabling highly selective photocatalytic semi-hydrogenation of alkynes.

The transformation of N₂ into high-value nitrogen-containing organic compounds is of great significance and compared with d-block metals, the derivatization chemistry of rare-earth metal dinitrogen complexes remains elusive. Here, the authors report the formation of oxadiazoles promoted by multinuclear samarium [(N₂)^4-] species.

The oxyhalogenation of methane to mono-halogenated products CH₃X (X = Cl, Br, or I) is among the most promising routes for methane utilization, yet current catalysts still suffer from limited product yields. Here, the authors report a CeO₂ nanorod catalyst with atomically dispersed Pd and Mn surface sites, which achieves highly efficient and selective methane oxychlorination.

The oxidative intermolecular amination of C-H bonds represents a straightforward method to construct aliphatic allylic amines. However, the utilization of widely available internal alkenes remains a synthetic challenge. Here, the authors present a regioselective Cu-catalyzed oxidative allylic C-H amination of internal olefins with azodiformates.

C-oligosaccharides are found in natural products and drug molecules, but their synthesis is challenging. Here, the authors report a strategy for the stereoselective and efficient synthesis of Coligosaccharides via palladium-catalyzed nondirected C1–H glycosylation/C2-alkenylation, cyanation, and alkynylation of 2-iodoglycals with glycosyl chloride donors.

Polysubstituted arenes are ubiquitous structural cores in natural products and drugs but their synthesis through programmable arene modification remains a challenge. Now, a palladium- and norbornene-catalysed Catellani-type reaction of aryl ketones, through successive acylation and deacylation, allows the synthesis of polysubstituted arenes.

Introducing and stabilizing oxygen vacancies within oxide supports remains a significant challenge for enhancing catalytic activity in redox reactions. Here, the authors fabricate centimeter-scale porous single-crystalline Nb₂O₅ monoliths and deposit Pt clusters on their surfaces, creating an interfacial system that markedly improves catalytic CO oxidation.

Improving catalysts for producing carbonates remains a challenge due to limited activity and durability. This study shows a bismuth–ceria catalyst that enhances reaction steps through remote electronic effects and can be easily regenerated.

Turning biogas into high-quality methane is limited by inefficient catalysts and complex processing. This study shows that a CeZrO_x/Ni inverse catalyst enables near-complete conversion in a simpler single stage, lowering costs and boosting viability.

Nature’s redox enzymes inspire the design of catalysts with precise spatial control. Here, the authors report stable metal-free bicarbenium catalysts that form biradicals for highly selective oxygen and nitric oxide reduction, revealing a blueprint for open-shell electrocatalysis.

Proton-exchange membrane water electrolysers rely on iridium to catalyse their anodic reaction, and while ruthenium is a less costly alternative due to its similar activity, it is not as stable. Now, a hierarchical machine-learning catalyst discovery workflow, termed mixed acceleration, is put forward to predict catalyst synthesis, activity and stability, and identify promising RuO_x-based water oxidation catalysts.

Heavier group 14 carbene analogue display remarkable capability for small molecule activation but their application in redox catalysis remains elusive. Here, the authors report the synthesis and isolation of a stannylene with carbodiphosphorane ligand and characterize its catalytic activity in the hydrodefluorination reaction of fluoroarenes.

The implementation of asymmetric Heck/cross coupling cascades of highly flexible haloalkene substrates remains a challenging and long-standing goal. Here the authors report an asymmetric domino Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes enabled by palladium catalysis.

Catalytic asymmetric click reactions of azides and alkynes for chiral triazole synthesis remains a challenge, due to the limited catalytic systems and substrate scope. Herein, the authors report the enantioselective azidation/click cascade reaction of N-propargyl-β-ketoamides via copper catalysis, affording a variety of chiral 1,2,3-triazoles.

Developing skeletal editing tools, especially to realize the single-atom transmutation in a ring system without altering the ring size is challenging. Here, the authors introduce a skeletal editing strategy that enables polycyclic arenols to be readily converted into N-heteroarenes through carbon–nitrogen transmutation.

Angular tricyclic and polycyclic skeletons feature typical cores in an intriguing type of natural products. Herein, the authors report Lewis acids catalyzed dearomative (3 + 2) cycloadditions of donor-acceptor cyclopropanes with benzene ring for the synthesis of diverse angular tricyclic and polycyclic carbocycles.

Hydrodeoxygenation (HDO) of phenolics is essential for converting lignin into fuels via fast pyrolysis, but catalyst deactivation from coking remains a major challenge. Here, the authors present a TiO_x-decorated NiSn/SiO₂ catalyst that delivers 100% deoxygenation selectivity and significantly improved stability in the HDO of m-cresol.

Selective catalytic reduction of NOx to N₂ using methanol as the reductant (Methanol-SCR) offers a promising route for eliminating NOx emissions from methanol engines and coal-fired power plants, but its performance at low temperatures remains limited. Here, the authors identify a strategy to enhance low-temperature Methanol-SCR activity through the cooperation between zeolitic acid sites and single iron redox sites.

Metal–sulfur motifs are commonly found in enzymatic active sites and heterogeneous catalysis, but they remain underexplored in porous solids. Now, sulfur-based ligands have been incorporated into metal–organic frameworks through post-synthetic modifications. The resulting sulfide MOFs exhibit enhanced catalytic performance in the selective hydrogenation of nitroarenes compared with their parent MOFs containing terminal or bridging chloride and hydroxyl groups.

The lack of efficient and diverse synthesis strategy has hindered the study of perifused cycles. Here, the authors report a metal-catalyzed cascade electrocyclization to access 5,6,7-perifused cycles, and demonstrated the versatility of this protocol in the late-stage modification of pharmaceuticals.

The development of catalysts for practical asymmetric hydrogenation of ketones remains an important goal of synthetic organic chemistry. Here, an anionic iridium catalyst with excellent activity is reported and used in a hundred-kilogram-scale reduction as part of a route to chiral nicotine.

Creating highly active materials that effectively harness solar spectra is essential for photocatalysis, though challenging. Here the authors introduce a novel donor-acceptor covalent organic framework with a broad absorption range of 200 nm to 900 nm, achieving efficient artificial photocatalytic amine coupling.

Saturated three-dimensional carbocycles have gained increasing prominence in synthetic and medicinal chemistry. Here, the authors present facile access to a variety of bicyclo[2.1.1]hexanes via a stepwise two-electron formal (3 + 2) cycloaddition between silyl enol ethers and bicyclo[1.1.0]butanes under Lewis acid catalysis.

Allylic substitution reaction of alkenes has been well-developed, but it has limitations, partly due to the intrinsic predilection for an inner-sphere mechanism. Herein, the authors present an outer-sphere mechanism in Rh-catalyzed allylic substitution reaction of simple alkenes using gem-difluorinated cyclopropanes as allyl surrogates.

This work demonstrates how engineered dipole synergy between two semiconductor materials creates efficient charge transport pathways, enabling simultaneous production of clean hydrogenand high-value chemicals from solar energy.

Cobalt-zeolite catalysts for propane dehydrogenation (PDH) typically exhibit low activity due to the confined Co sites within the zeolite framework or poor stability of CoO_x species under hydrogen. Here, the authors demonstrate that anchoring CoO_x nanoclusters onto the 10 -membered rings of silicalite-1 significantly enhances PDH performance.

The rational design of efficient propylene epoxidation catalysts is hindered by the unclear catalytic mechanism. Here, using in-situ spectroscopy to probe the supported single-Ag-atom catalyst, the authors report a dual-site synergistic mechanism for the electrocatalytic propylene epoxidation.

Subsurface structure dictates the catalytic activity in heterogeneous catalysis. Here, the authors report an atomic diffusion pathway mediated subsurface engineering strategy, enabling precise control of subsurface atomic layers in Pt-based intermetallic compounds.

Selective CO₂ hydrogenation to C₂₊ oxygenates is difficult due to competing pathways. A tandem GaZrO_x–MOR system enables efficient acetic acid and methyl acetate synthesis, using hydrophobic modification to enhance stability and water resistance.

Templated synthesis is a valuable method for the preparation of oligomers but requires stoichiometric amounts of the template. Here a catalytic macrocyclic template is reported that promotes the oligomerization of a small-molecule substrate and controls its length. The length of the oligomer correlates with the dimensions of the template.

The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities, but often require an inert atmosphere to maintain high efficiency. Here, the authors develop a photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems.

Exploitation of noncovalent interactions has received much attention for the design of metal catalysts. However, because of the weak nature, CH-π interactions have been less utilized for the control of organic reactions. Here, the authors report that the CH-π interaction can be used to kinetically accelerate catalytic C-H activation of arenes.

Tuning the adsorption–desorption behavior of molecules on solid catalysts is crucial for achieving complex catalytic functions. Here, the authors show that Gaussian curvature engineering of self-pressurizing mesoporous nanoreactors enhances the dynamic equilibrium between molecular adsorption and desorption.

Atomically dispersed catalysts show promising activity for electrochemical reactions but often suffer from limited stability. Here, the authors report an atom-ordering strategy that forms triangular Co sites to activate the substrate for durable alkaline hydrogen production.

Asymmetric intermolecular hydroamination of alkenes is a challenging process, potentially leading to useful chiral amines. Here, the authors report unsymmetric NNN tridentate ligands promoting the cobalt-catalyzed radical hydroamination of alkenes via hydrogen atom transfer, also in an asymmetric fashion.

One strategy to address multidrug resistance in cancer is the development of modular methods to access bioactive scaffolds. Here, the authors report a Rh(III)-catalyzed carboxylic acid-directed C(sp²)−H allylation and apply it to the modular synthesis of (Z)-allylic macrolides which enhance antitumoral drug activity.

Homoenolates and their higher homologs have much potential, albeit largely unrealized, in transition metal catalysis. Here, the authors report the nickel-catalyzed generation of homoenolates, and their higher homologs, via decarbonylation of cyclic anhydrides, which then undergo cross-coupling with alkyl bromides.

Acid chloride formation is generally limited to the chlorination of carboxylic acids. Here, the authors report a palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for the synthesis of various alkyl acid chlorides.

The difunctionalization of diazo compounds, traditionally with one nucleophile and one electrophile, is a powerful strategy. Here, the authors develop a path of electrochemical oxidative difunctionalization of diazo compounds with two different nucleophiles.

Despite the growing importance of fluorinated organic compounds introduction of fluorine into organic molecules is still challenging. Here, the authors present the development of palladium and phosphine synergistic redox catalysis of fluorocarbonylation of potassium aryl/alkyl trifluoroborate.

Developing efficient non-precious catalysts is key to advancing water electrolysis. Here, the authors report a microbial vulcanization strategy that co-dopes cobalt hydroxide with sulfur and organic molecules to optimize O–O coupling and accelerate the electrocatalytic oxygen evolution reaction.

Design of hydrogen evolution catalysts needs to balance the hydrogen adsorption energy to facilitate easy adsorption and desorption. Here, the authors report a composite catalyst where hydrogen adsorption occurs on rhodium and desorbs from silicon which has a lower adsorption energy.