ACS Catalysis

Of central interest in plasmonic photocatalysis is efficiency, defined as the ratio of the rate of chemical transformation to the power of the incident light. Efforts to enhance efficiency have focused largely on optimizing the photocatalyst structure and composition, reaction conditions, and reactor design. Here, we show that the temporal distribution of incident photons is another parameter tha…

The rational modulation of catalysts with efficient hydrogen activation and controllable management properties is essential to improve the hydrogenation performance. Herein, we have employed a gradient diffusion-in situ reconstruction strategy to prepare the YS-Co3S4@AlO-CoMoS catalyst with an efficient hydrogen spillover network. The coordinated dissociation of Co-hybrid nanospheres during sulfi…

The use of C1 molecules as feedstocks for producing high-value chemicals is an attractive yet technically inefficient process. Optically pure α-arylglycines are valuable pharmaceutical intermediates, but their efficient asymmetric biosynthesis from C1 molecules has not been reported. Herein, a multienzyme biosynthetic pathway was successfully designed and implemented for the asymmetric synthesis …

We introduce 1, a (pyridyl)-N-heterocyclic carbene-ligated ruthenium(II) homolog of catalyst 2, and show that the NHC ligand prevents catalyst cluster formation and catalyst death while changing the rate-determining step to imine hydrogenation. We previously introduced (pyridyl)phosphine-ligated ruthenium(II) precursor (2) as a hydrogen-borrowing amination catalyst, but it undergoes carbonylative…

Chiral organosilicon compounds featuring a silicon-stereogenic center have attracted renewed interest in recent years. However, the enantioselective synthesis of such molecules containing both carbon and silicon stereocenters from prochiral precursors remains a significant challenge. Herein, we report a desymmetrization strategy that enables the simultaneous construction of two adjacent stereocen…

We report a Cu-catalyzed C−N cross-coupling of (hetero)aryl chlorides with a broad range of nitrogen nucleophiles. Nucleophiles include primary, secondary, and α-branched amines; amides; hydrazines; ammonia surrogates; NH-heterocycles; and base-sensitive substrates such as aminomethyl-functionalized azoles. Aryl and heteroaryl halides, including pyridyl and pyrimidyl chlorides, are competent reac…

Methane Steam Reforming (MSR) is a critical process for hydrogen production in the chemical industry. Nickel-based catalysts are usually preferred for MSR due to their high activity and low cost. Several studies have shown that step edges and defects on Ni surfaces have a strong influence on the MSR kinetics. However, a detailed mechanistic-level understanding of the MSR reaction on stepped Ni su…

The chemical inertness of polyolefin plastics poses a significant challenge to their efficient recycling. In this work, a Ru/TiO2-CNT catalyst is developed by engineering interfacial compatibility and dynamic active hydrogen pools to accelerate polyolefin hydrogenolysis. Enhanced interfacial compatibility between Ru and TiO2 optimizes the electronic state of Ru, thereby facilitating effective C−C…

Non-oxidative propane dehydrogenation (PDH) to propene is the basis of several technologies developed for meeting the increasing demand for this olefin. Given the high cost of commercial Pt-based catalysts, a promising direction for improving the economics of propene production by PDH is to reduce Pt content without sacrificing high propene productivity and selectivity. We report that the 1Co-0.1…

The conversion of C–H bonds into amines by nitrene insertion is an attractive transformation since it is both atom- and step-economical, and provides a direct route to functionalizing hydrocarbons. Using an iron catalyst [{(tBupyrr)2pyr}Fe(OEt2)] (1-OEt2) ((tBupyrr)2pyr2– = 3,5-tBu2-bis(pyrrolyl)pyridine), we recently demonstrated the catalytic conversion of weak C–H bonds into secondary amines u…

We report herein a general palladium-catalyzed enantioselective three-component reaction of N-sulfonylhydrazones, aryl halides, and cyclopropanols. This modular method enables the efficient one-pot synthesis of enantioenriched γ,γ-diarylcarbonyl scaffolds with high stereoselectivity. Key advantages include readily available substrates and broad functional group tolerance. Combined experimental an…

Rational design of photocatalytic systems coupling the reduction of CO2 with water oxidation is vital for carbon-neutral technologies. Herein, we propose a strategy based on the synergistic assembly of polyoxometalates (POMs) within and on a porphyrinic metal–organic framework (MOF, PCN-222). Cross-scale integration of an S-scheme heterojunction and a molecular junction within a single POM@MOF-PO…

A highly enantioselective reduction of prochiral 2H-azirines has been achieved, mediated by chiral copper-hydride complexes. Both alkylated and arylated mono- and trisubstituted 2H-azirines are reduced to afford N–H aziridines in high yields (up to 96%) and enantioselectivities (up to 96% ee). Such aziridines are building blocks of wide synthetic utility, and to demonstrate this, we executed a gr…

Large language models (LLMs) have demonstrated their limitations in addressing the design of active proteins that rely on intricate intramolecular interactions, particularly in the engineering of biocatalysts. Conducting real-world studies from targeted laboratory assays has become the de facto standard for artificial intelligence (AI) research in complex biological tasks. In this study, we prese…

Hydrogen binding energy (HBE) is a key thermodynamic descriptor for the hydrogen oxidation reaction (HOR), yet its influence on the interfacial water structure in the electric double layer (EDL) and reaction kinetics, particularly as modulated by adsorbed hydrogen (Had) coverage, remains poorly understood. Here, we employ a WO3-supported Ir nanoparticle catalyst (WO3–Ir) to elucidate the impact o…