Anion exchange membrane water electrolysis (AEMWE) is a promising technology for sustainable hydrogen production, yet limited OH− supply at the anode remains a key challenge. Zhu et al. report a high-valence Lewis-acid-enriched perovskite anode with fast OH− adsorption and reveal the direct participation of surface hydroxyls in alkaline OER.
Photocatalytic nitrogen fixation offers a sustainable alternative to the energy-intensive Haber-Bosch process but remains limited by inefficient N2 adsorption and activation. Here, we construct atomic iron (Fe)-based frustrated Lewis pairs (Fe···OHSA FLPs) on defective bismuth (Bi)/bismuth oxybromide (BiOBr), where isolated Fe sites and surface hydroxyl groups function as Lewis acid and Lewis base centers, respectively. Characterizations and theoretical calculations reveal that the Fe···OH FLPs synergistically strengthen N2 adsorption, facilitate N≡N activation, and promote proton-coupled electron transfer. Consequently, the optimized catalyst achieves an ammonia (NH3) production rate of 502.64 μmol g−1 h−1 under sacrificial-agent-free conditions, representing a 13.96-fold enhancement over BiOBr. Mechanistically, oxygen-vacancy-induced tetracoordinated Fe decreases the crystal-field splitting between the t2g and eg orbitals, forming a high-spin electronic configuration. The resulting enhanced Fe 3d-N2 2p orbital coupling promotes electron transfer into antibonding orbitals and accelerates N≡N bond cleavage. This work establishes spin-state engineering as an effective strategy for activating N2 on single-atom-based FLP photocatalysts.
Selective termination of carbon-centered radicals under electrochemical conditions remains challenging, particularly in strained systems where over-reduction and unselective quenching can compete with productive atom transfer. Herein, we report an electrochemically enabled atom-transfer radical bromoalkylation of [1.1.1]propellane that converts activated alkyl bromides into isolable, bench-stable 1-alkyl-3-bromobicyclo[1.1.1]pentanes. Constant-current electrolysis with a zinc anode, nickel-foam cathode, and tetrabutylammonium bromide electrolyte initiates alkyl radical formation while favoring bromine atom transfer to the bicyclopentyl radical intermediate. The reaction accommodates primary, secondary, and tertiary activated alkyl bromides, including complex drug-like substrates, and the resulting BCP–Br products undergo C-, B-, P-, Se-, O-, and N-functionalization. Mechanistic experiments, including radical-clock and radical-trapping studies, cyclic voltammetry, and charge analysis, are consistent with an electrochemically initiated ATRA chain. This method provides a modular entry to brominated BCP linchpins and illustrates how electrochemical initiation can guide radical reactivity in strained molecular scaffolds.
Yongli Cai is an associate professor at the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences, where she studies the conversion of dinitrogen into nitrogen-containing compounds. Jianping Guo is a professor at the Dalian Institute of Chemical Physics, and his research aims to elucidate the distinctive properties of hydride, amide, and imide materials. Ping Chen is a professor at the Dalian Institute of Chemical Physics and director of the Hydride Energy Research Center. Her research encompasses hydrogen storage, hydride-mediated dinitrogen fixation, and hydride ion transport and focuses on developing hydride chemistry for sustainable energy conversion and utilization.
Iron-based catalysts with strong oxophilicity typically induce inert O-end adsorption of nitrogen-containing intermediates, severely constraining C‒N coupling efficiency in urea electrosynthesis. To break this thermodynamic limit and actively invert the adsorption configuration, we deliver a “geometry-spin” synergistic strategy to construct a surface-segregated Cu‒Fe@NC bimetallic electrocatalyst. Cu‒Fe interfacial tensile strain and orbital hybridization induce Fe-site spin depolarization, forming an atomic “spin-valve” for enhanced NO3−/CO2 co-reduction. It achieves 61.8% urea Faradaic efficiency, with remarkable yields of 2,273.7 and 21,176.7 μg h−1 mg−1 in H-type and flow cells, respectively. Mechanistic investigations elucidate that surface segregation optimizes spatial distance for Cu-activated ∗CO and Fe-immobilized ∗NO2; meanwhile, Cu incorporation realigns Fe d-band center toward the Fermi level, promoting ∗NO2 inversion to active N-end adsorption, thereby reducing the C‒N coupling kinetic barrier for urea electrosynthesis. This work offers a universal paradigm for oriented electrosynthesis by leveraging the geometry-spin coupling effect to reverse the adsorption configuration of key intermediates.
Efficient and highly stereoselective synthesis of bicyclo[2.1.1]hexanes (BCHs) is crucial for their application as bioisosteres of aromatics in medicinal chemistry. We employed a chiral tetracoordinated boron catalyst in asymmetric [2π+2σ] cycloaddition of bicyclo[1.1.0]butane (BCB) to establish the BCH framework. This study demonstrates for the first time the potential of chiral tetracoordinated boron catalysis in activating BCBs, augmenting activation modes, and broadening applications. The reaction, generated in situ from commercially available BINOL (1,1'-bi-2-naphthol) derivatives under mild conditions, proceeds with excellent yields, up to 99% enantiomeric excess (ee) and >20:1 diastereomeric ratio (dr), enabling synthesis of chiral BCH derivatives. The methodology is practical and scalable, allowing gram-scale synthesis and conversion to drug analogs. Mechanistic and density functional theory (DFT) studies indicate that the rigid chiral catalyst creates a confined chiral environment where electronic and steric factors determine enantioselectivity and diastereoselectivity.
Spin modulation is a tunable strategy for enhancing activity and mechanistic diversity in Ni-based methanation and other catalytic reactions by magnetic metals. In this issue of Chem Catalysis, Nørskov and co-workers show that adsorption-induced spin quenching of surface magnetism provides a broadly applicable pathway for designing advanced spin-engineered catalytic materials.
In a recent issue of Science, Yoon, Zysman-Colman, and co-workers report modular chiral pybox photocatalysts via a three-step synthesis from chiral pool materials. These catalysts incorporate electron-donating carbazole units for tunable charge-transfer (CT) photochemistry and show generality in three model asymmetric reactions, including photoredox and excited-state photoreactions.
In a recent issue of Nature Catalysis, Boniface et al. use operando techniques to gain new insights into how classical Cu/ZnO/Al2O3 catalysts operate in methanol synthesis, significantly advancing our understanding of their behavior. These catalysts function as a dynamic ensemble of Cu, ZnOx ultrathin films, and Cu–Zn alloy phases that continuously interconvert under reaction conditions. However, the atomistic nature of the active site remains elusive.
By engineering the copper catalyst for electrocatalytic CO2 reduction with nonmetal elements, the local coordination microenvironment of active sites can be optimized, leading to enhanced efficiency for C2+ products. This review aims to systematically summarize recent advances in promoting electrocatalytic CO2 reduction to C2+ products through nonmetal doping for tuning the coordination microenvironment of copper-based catalysts. We will first discuss engineering strategies for doping nonmetal elements into copper catalysts. Subsequently, we will analyze how various nonmetal dopants modulate the coordination microenvironment and electronic structure of copper active centers. Special emphasis will be placed on elucidating how these nonmetal elements influence the intermediates and the C–C coupling step during the CO2 reduction process, enabling selective control over C2+ product formation. Finally, the key challenges and future directions in this field are provided. Mechanistically, this review reveals structure-activity relationships to provide insights and theoretical guidance for designing efficient copper-based CO2 reduction catalysts.
Ir-catalyzed asymmetric allylic substitution (AAS) reactions have long been recognized as an efficient method for the synthesis of chiral functionalized olefins. The most studied reaction patterns feature an E-to-B or B-to-B pathway that transforms linear E-allyl or branched allyl electrophiles into chiral branched olefin products. In this work, we present a strategy for realizing E-to-Z or E-to-E transformations with the Ir-catalyzed AAS reaction as a key step. With 3-isochromanones as the prochiral nucleophiles under similar conditions, chiral Z/E olefin products were selectively achieved from aryl/alkyl-substituted allyl electrophiles in high yields and stereoselectivity (up to 97% yield, >20/1 Z/E, >20/1 L/B [linear to branched] and 90% enantiomeric excess [ee] for Z products; up to 95% yield, >20/1 L/B and 96% ee for E products).
Cu single-atom catalysts exhibit great potential for CO2 reduction, but their intrinsic roles under realistic conditions remain debated. Herein, we present compelling evidence elucidating the active sites of Cu-TiO2 single-atom catalysts for CO2 photoreduction with H2O. In situ X-ray photoelectron and infrared spectroscopy reveal that H2O molecules adsorbed at Cu sites inject electrons to induce low valence states, thereby promoting CO2 adsorption on adjacent Ti sites and driving them toward high oxidation states. Under illumination, the CO2 molecules on Ti sites transformed into ∗COOH and CO∗ intermediates, while the H2O molecules dissociated into the OH group on Cu sites to produce protons and electrons. Accordingly, their cooperative catalysis remarkably enhances CO2-to-CO conversion activity (161.1 μmol g−1 h−1), far exceeding that of pristine TiO2 (31.8 μmol g−1 h−1). These findings challenge the conventional speculations on single-atom Cu catalysts and provide new insights for the re-evaluation of static structure-activity models.
In Chem, Liu et al. demonstrate that an Ag/Cu metal superlattice electrocatalyst enables the stable conversion of CO2 to the bioproduct 3-hydroxypropionic acid through an integrated electrochemical-microbial system (iEMS). A preliminary techno-economic analysis estimates that the iEMS could generate annual profits about 15-fold greater than those estimated for a standalone electrocatalytic system while reducing carbon emissions relative to those of incumbent production methods.
Carbon support engineering is used to improve mass transport and long-term durability in proton-exchange membrane fuel cell (PEMFC) catalyst layers. This perspective reviews structural design approaches such as hierarchical pore architectures and graphitized core-shell composites, as well as surface functionalization with heteroatoms including N, F, and Br. These strategies are discussed in relation to oxygen and proton transport resistance, three-phase boundary formation, and ionomer distribution. Mechanistic insights from in situ characterization and modeling are used to connect carbon morphology and interfacial chemistry to carbon corrosion pathways and stability under electrochemical operation. This perspective provides a rationale for selecting support structures and functional groups to mitigate corrosion while maintaining efficient transport, supporting the development of scalable high-performance PEMFC systems.
Hao Li is a Distinguished Professor at the Advanced Institute for Materials Research (WPI-AIMR) of Tohoku University. His research focuses on developing artificial intelligence (AI), materials theory, and autonomous experimentation for closed-loop materials design. He also serves as the founding editor-in-chief of the journal AI Agent. Di Zhang is a Distinguished Assistant Professor at the Frontier Research Institute for Interdisciplinary Sciences (FRIS) of Tohoku University. His work centers on digital catalysis platforms, catalytic databases, machine learning, and AI agents for data-driven materials discovery.
