Metal-organic frameworks (MOFs) often undergo structural reconstruction during oxygen evolution, but controlling this transformation remains challenging. Here, we demonstrate that Cr incorporation into a Hofmann-type MOF regulates local coordination and directs surface-selective reconstruction into active oxyhydroxide species while maintaining framework integrity. This Cr-mediated strategy converts uncontrolled MOF degradation into a controllable activation process, enabling efficient oxygen evolution and high-performance anion-exchange membrane water electrolysis.

Conventional catalysts for CO2 hydrogenation often rely on separate energy-intensive hydrogen pre-treatments to generate their active phases. Here, iron-based spinel oxides bypass this step by restructuring under reaction conditions to form exsolved anchored metal nanoparticles and iron carbides that enhance short-chain hydrocarbon production. This self-activation strategy provides a simpler, more energy-efficient route to catalyst design.

Bayesian optimization (BO) is an efficient reaction optimization strategy for organic chemistry that is seeing increasing adoption in the field. This perspective aims to lower the entry barrier for first-time users by providing a step-by-step guide toward getting started.

We report a biomimetic superhydrophobic anode that minimizes H2O2-electrode interactions through a weak-adsorption interface, exhibiting excellent durability over 30 h and readily scalable to a 300 cm2 electrode, enabling H2O2 accumulation exceeding 50 mM within 1 h.

A triple-regulation strategy integrating heteroatom doping, interface engineering, and substrate loading modulates electronic structure, accelerates electron transport, and optimizes intermediate adsorption to achieve high-efficiency HER catalysis.

Plasma-#catalytic CO2 hydrogenation studies commonly report high CH3OH selectivities using a subtraction-based offline analysis, which assumes a closed carbon balance. Using a direct online GC quantification across two laboratories, this work shows that CH3OH selectivities are greatly overestimated by the subtraction-based offline quantification. CH3OH co-feeding experiments and kinetic modeling reveal that microdischarge-induced heating and radical chemistry drive rapid CH3OH decomposition. This work highlights the importance of rigorous, direct online product quantification in plasma catalysis.

Turing-patterned SrIrO3 stabilizes high-valent Ir for acidic OER. Coupling the self-organized grain-boundary architecture with mechanical strain tunes neighboring Ir interactions and redirects the OER pathway, thereby enabling simultaneously enhanced activity and durability. This work establishes a structurally responsive strategy for oxide #electrocatalysis.

Selective control of reactive oxygen species is essential for efficient photocatalytic oxidation. This study demonstrates that crystal facets and oxygen vacancies can cooperatively regulate oxygen activation on metal oxide surfaces, thereby enabling direct non-radical conversion of oxygen into singlet oxygen. The strategy provides a general approach for designing photocatalysts with controllable oxidation pathways.

Hydrogen peroxide (H2O2) is sustainably generated through two-electron oxygen reduction reaction (2e‒ ORR) and water oxidation reaction (2e‒ WOR) pathways. The resulting H2O2 serves as a versatile green oxidant for valuable chemical transformations, including olefin oxidation, cyclohexanone ammoxidation, biomass upgrading, and C‒H oxidation. This integrated platform highlights the potential of electrochemical H2O2 production to enable efficient and environmentally responsible oxidative synthesis.

In this work, the authors develop an atomically dispersed Ru catalyst on a niobium nitride support (RuSA-Nb4N5) for highly efficient hydrogen evolution reaction. They uncover a synergistic multi-site Volmer-Heyrovsky (V-H) mechanism where Ru and Nb act as “molecular scissors” to cleave water, while the electronically awakened lattice nitrogen atoms serve as optimal sites for hydrogen desorption. This distinctive metal-nitrogen cooperative paradigm overcomes traditional scaling relations, providing a highly competitive catalyst and new insights for industrial water electrolysis.

Rh-Fe intermetallic catalysts supported on MCM-41 enable highly efficient heterogeneous olefin hydroformylation through composition-dependent electronic regulation of Rh active sites. Combined spectroscopic characterization, kinetic analysis, and DFT calculations reveal that #catalytic activity is governed by a delicate adsorption-activation balance, leading to a volcano-shaped activity trend with Rh1Fe1 as the optimal catalyst.

Rigorous evaluation of catalyst stability and understanding short- and long-range structural evolution are critical for the CO2 reduction reaction. Using time-resolved in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD), we report a three-stage, potential-dependent evolution of zeolitic imidazolate framework-8 (ZIF-8), providing direct insight into its instability behavior.

Gold nanoparticles were introduced into the periplasmic space of a non-electroactive microbe, Ralstonia eutropha, as a conductive bridge for microbial CO2 conversion, with enhanced delivery of external electrons into cellular metabolism. This biohybrid system not only showed improved CO2 reduction performance but also regulated product selectivity by the processing method of bioelectrodes. While drop-casted electrodes produce acetate, self-assembled biofilms yield a C4 product, β-hydroxybutyrate, with over 90% selectivity.

Anion-exchange membrane water electrolyzers could enable low-cost hydrogen production, but building durable, efficient membrane-electrode interfaces remains challenging. We design a conjugated polymer interlayer that allows catalysts to grow directly on the membrane without catalyst-layer ionomer binders, thereby reducing interfacial resistance and improving durability through an alkaline-responsive protective interface.

Graham et al. have engineered a thermostable polyurethane (PUR)-degrading enzyme through molecular-dynamics-guided design, establishing a versatile scaffold for biocatalysis. Targeted active-site mutations enhance hydrophobic interactions and introduce π-π stacking, resulting in a 20-fold increase in #catalytic efficiency. This work lays a strong foundation for developing next-generation enzymes capable of tackling recalcitrant PUR waste.

Integrating pillar[5]arenes into covalent triazine polymers creates a molecular-level built-in electric field. This polarization design facilitates rapid charge transfer, enabling efficient H2O2 production from pure water without sacrificial agents. This work highlights the potential of macrocyclic chemistry to precisely tailor charge dynamics in polymers for diverse photocatalytic applications.

Electrochemical CO2 reduction to methanol requires both binding of the CO intermediate and its subsequent protonation. Ligand isomers of tetraamino-substituted cobalt phthalocyanine reveal that interfacial water structure, beyond CO binding strength, governs how readily the CO intermediate is protonated and thereby steers methanol production.

A unimolecular precatalyst integrates light activation and #catalytic functions within a single molecule, thereby enabling cooperative radical processes for C–H oxidation and polymer degradation. This strategy provides a new approach for designing self-contained #catalytic systems with programmed reactivity.

This review examines the scale-up of photoelectrochemical water splitting from laboratory-scale to large-area photoelectrodes, integrated devices, and outdoor systems. It highlights key challenges arising during scale-up, including nonuniform fabrication, resistive losses, gas crossover and bubble management, and long-term durability. Recent advances in scalable fabrication, reactor and device engineering, and outdoor operation are discussed, together with future priorities for bridging laboratory performance and commercially relevant solar hydrogen production.

Hydrogen production powered by intermittent energy sources relies on the dynamic stability of catalysts undergoing reverse polarization during shutdown conditions. This study on thin-film NixFe(1–x)OOH reveals that anode catalyst degradation depends on how long the electrode stays in the reduced state, due to the loss of iron from the film. X-ray photoelectron spectroscopy quantified the surface iron content, and in situ Raman spectroscopy monitored changes in the catalyst phase during reverse polarization.

We report a copper-catalyzed hydrodimerization of 1,3-enynes that employs CO2 as a molecular “bridge” to construct C2-symmetric chiral alkynylols with high enantioselectivities, even at low CO2 concentration. Mechanistic studies reveal a key aldehyde intermediate in forming the CO2-linked homocoupling product. This strategy introduces a distinct mode of CO2 utilization and provides chiral monomers for copolymerization and homopolymerization, connecting asymmetric catalysis with the development of functional chiral materials.

Decoupled electro-biosystems link renewable electricity and CO2 conversion with biological upgrading. This perspective introduces the “electrofuel recipe” concept, in which electrochemically generated intermediates are tailored to serve distinct carbon and energy functions. By matching intermediate composition, conditioning, and flux to biological demand, this framework offers new opportunities to improve carbon utilization and guide catalyst, reactor, and process design for zero-carbon biomanufacturing.

Molecular catalysis offers a fundamentally different strategy for regulating iodine chemistry in aqueous zinc-iodine batteries beyond conventional confinement approaches. This commentary outlines three molecular regulatory dimensions and highlights key design principles for developing next-generation catalysts for complex electrochemical conversion reactions.

Engineering cooperative dual active centers offers a powerful strategy to control molecular activation and reaction pathways for selective hydrogenation of unsaturated functional groups.

This study presents a simple and efficient method for the selective deuteration of azines at their metabolic soft spot, including pharmaceutical compounds, relying on the in situ generation of nickel nanoparticles using deuterium gas as the isotopic source. While the broad substrate scope, excellent functional group tolerance, and ease of implementation of this method demonstrate its potential to accelerate the development of deuterated drugs, we further demonstrated that precise deuterium incorporation can serve as a strategic tool in prodrug design.

Natural nicotinamide cofactors are often unstable under demanding biocatalytic conditions. This study reports CNMN+, a thermostable artificial nicotinamide mononucleotide with a more negative redox potential than NADP+ and NMN+, together with engineered systems for its synthesis and regeneration. Coupling this platform with hydrogen-evolution and alkene-reduction reactions demonstrate how integrated cofactor design and enzyme engineering can enable redox biocatalysis at elevated temperatures.

Atomic Fe-based frustrated Lewis pairs were fabricated on defective Bi/BiOBr that exhibited enhanced photocatalytic NH3 synthesis. Oxygen vacancy-induced tetracoordinated Fe facilitates the generation of high-spin electrons via reducing the orbital-splitting energy between eg and t2g orbitals, thus enabling targeted capture and activation of N2 through d-p orbital interaction.

Electrochemical initiation converts activated alkyl bromides and [1.1.1]propellane into bench-stable alkyl–BCP–Br linchpins through radical-chain atom-transfer bromoalkylation, enabling late-stage and divergent diversification.

Mechanical force provides a distinct route for controlling catalysis by directly coupling chemical function with material deformation. This commentary defines polymer mechanocatalysis through two modes of force-catalysis coupling: transient activation and persistent regulation. We discuss how polymer architectures enable force transmission at the molecular level and outline emerging strategies for converting mechanical force from a trigger into a programmable variable that controls #catalytic behavior.

Main-group metal hydrides provide a distinctive platform for probing the fundamental synergistic reactivity of hydride anions and main-group elements in dinitrogen (N2) conversion. This commentary surveys thermocatalytic, chemical-looping, and external-stimuli-driven pathways for N2 transformation; analyzes key unresolved challenges; and proposes material design strategies to advance the mild conversion of N2 to ammonia for renewable-energy storage.

Understanding why oxide electrocatalysts dissolve under acidic oxygen evolution conditions is essential for designing durable water electrolysis catalysts. Wang et al. develop a thermodynamic framework that quantitatively relates oxide composition to electrochemical stability, enabling prediction of stability trends beyond existing materials databases and providing general design principles for discovering more durable oxide electrocatalysts.

An atomic Cu‒Fe “spin valve” is presented to induce spin depolarization at Fe sites through interfacial strain regulation and orbital hybridization. This enables a precise asymmetric charge distribution on the C-/N-intermediates of CO2/NO3− co-electrolysis, efficiently alleviating their electrostatic repulsion and steric hindrance during co-adsorption. Such spatial and electronic modulation reverses the adsorption configuration of the key ∗NO2 intermediate from O- to N-terminal binding on Fe sites, thereby markedly reducing the energy barrier for C–N coupling with Cu-reduced ∗CO. Accordingly, a high urea Faradaic efficiency of 61.8% is achieved, together with remarkable urea yields of 2,273.7 and 21,176.7 μg h−1 mg−1 in an H-type and flow cell, respectively.

Bicyclo[2.1.1]hexanes (BCHs) are valuable bioisosteres of aromatic rings in drug discovery, yet their asymmetric synthesis remains challenging. We report a chiral tetracoordinated boron-catalyzed asymmetric [2π+2σ] cycloaddition of bicyclo[1.1.0]butanes, enabling efficient construction of enantioenriched BCH frameworks with up to 99% ee and >20:1 dr. The mild, scalable protocol and mechanistic DFT studies highlight the potential of chiral boron catalysis in strained-ring chemistry.

An asymmetric electronic structure featuring Au–Cu alloy and adjacent Cu single atoms, constructed via a gradient alloying strategy, synergistically regulates charge separation and intermediate adsorption for highly efficient and selective photocatalytic methane oxidation to methanol.

The intrinsic symmetry of N2 limits its polarization and bond activation, while conventional average energetic descriptors fail to predict N2 activation behavior governed by pathway-dependent processes and site-specific interactions at #catalytic interfaces. This perspective introduces asymmetric-site catalysts as a design framework that breaks molecular symmetry through tailored local geometric and electronic asymmetry, creating nonequivalent interactions between nitrogen atoms to enable improved N2 activation and guide the rational development of efficient catalysts for sustainable nitrogen reduction.

Direct solar water splitting offers a promising route to sustainable hydrogen production, yet conventional photocatalytic systems remain limited by low areal productivity, large device footprints, and insufficient scalability. Photocatalytic water splitting under concentrated sunlight provides a compelling alternative by enabling high-throughput hydrogen generation on compact active areas while highlighting key future needs in photocatalyst films, reactor engineering, gas separation, and outdoor operational stability.

Water plays multiple roles in CoMn-based Fischer-Tropsch-to-olefin (FTO) catalysis. Fang, Li, Sun, and Wang discuss how physically mixed promoters with opposite wettability enhance #catalytic performance by regulating distinct water-mediated processes, including the accumulation of molecular water, catalyst phase evolution, and hydroxyl-mediated interfacial chemistry.

This review systematically summarizes recent advances in modulating the coordination microenvironment of copper-based catalysts via non-metal doping, spanning from engineering strategies to C–C coupling mechanisms, thereby providing a clear theoretical roadmap for the rational design of efficient CO2 reduction catalysts.

Olefin geometry profoundly dictates the properties of bioactive molecules, natural products, and organic materials. Herein, we describe a synthetic protocol enabling the selective construction of chiral Z/E olefins, with Ir-catalyzed asymmetric allylic substitution (AAS) as the pivotal step. By leveraging distinct E-to-E and E-to-Z pathways, this method affords the desired isomers with excellent selectivity.

An in situ spectroscopy study reveals distinct active sites and dynamic surface catalysis in single-atom Cu-TiO2 for CO2 photoreduction with H2O, challenging the conventional assumptions.

Classical pericyclic reactions such as 4π-electrocyclization and vinylcyclopropane rearrangement yield four- or five-membered rings. Now, a nickel-catalyzed 4σ-ring expansion of vinyl biscyclopropanes delivers six-membered cyclohexene-fused bicycles featuring challenging bridgehead quaternary carbons. The reaction is highly diastereoselective: cis-substrates give trans-products, and vice versa. Mechanistic DFT studies illuminate the sequential C–C cleavage events. This work expands the toolbox for ring expansion and offers a new entry to valuable fused bicyclic scaffolds.

Achieving green synthesis of biobased adipic acid instead of traditional two-step oxidation of petroleum-based cyclohexane advocates the principle of green and sustainable chemistry. Here, we present a MoOx-Pd/TiO2 catalyst that enhances the hydrodeoxygenation of 2-hydroxyadipic acid to adipic acid, which is achieved through hydrogen spillover from Pd to Mo sites and Mo-hydroxyl-mediated dehydration and hydrogenation. This work refines a biochemical synthesis route from glucose to adipic acid.

Carbon support engineering enhances mass transport and durability of PEMFC catalyst layers. This perspective reviews hierarchical pores, graphitized core-shell composites, and heteroatom (N, F, and Br) functionalization, linking these strategies to mass transport, triple-phase boundary, and ionomer distribution. Combined with in situ characterization and modeling, it provides rationale for anti-corrosion support design toward high-performance PEMFCs.

Converting carbon dioxide into useful chemicals using solar energy is a key strategy for a sustainable future. However, the natural rise and fall of sunlight throughout the day creates fluctuations that can damage solar-driven electrochemical devices. This study uses operando X-ray microtomographic imaging to show how electrodes fail under simulated diurnal irradiance. By revealing how liquids and salt precipitates build up inside the gas diffusion electrode, this work provides a roadmap for building more durable devices that operate reliably under real-world outdoor conditions.

This perspective examines the emerging capacity of achiral components—comprising hydrogen‑bonding donors, Brønsted acids, Lewis acids, and bases—to modulate enantioselectivity within N‑heterocyclic carbene (NHC) organocatalysis. Beyond the enhancement of stereoselectivity, these achiral species have been demonstrated to induce reversal of stereochemical outcomes, thereby facilitating enantiodivergent synthesis. Mechanistic rationales underlying these effects are discussed, with the aim of informing future reaction design and catalyst development.

We report a #photoredox arylbismacycle platform that enables controllable radical arylation through distinct Bi(III/IV) and Bi(V/IV) pathways. By tuning #photoredox quenching cycles, aryl radicals can be directed toward either nucleophilic or electrophilic reactivity, allowing selective functionalization of alkenes and arenes under mild conditions. This strategy expands main-group radical chemistry and provides a versatile approach to switchable bond-forming reactions relevant to synthetic and medicinal chemistry.

Faster quenching does not guarantee better catalysis. In photochemical systems, overall efficiency emerges from the interplay between photon flux, cage escape, and the kinetics of downstream reactions. We discuss how focusing solely on quenching can obscure other critical rate limitations and highlight the importance of synchronizing all elementary steps. This commentary advocates a holistic rate-matching strategy to optimize performance and guide the rational design of more efficient photochemical #catalytic processes.

Gas diffusion electrodes enable high-rate electrochemical CO2 conversion, but their long-term stability is limited by coupled transport and interfacial degradation. This review connects catalyst layer design, gas diffusion layer architecture, wetting behavior, and carbonate chemistry to electrode performance and durability, offering engineering principles for stable, high-performance CO2 electrolyzers.

A bio-inspired core-shell catalyst was developed for direct #electrocatalytic oxidation of N2 to nitrate. The crystalline ZnO shell acts as a selective barrier that concentrates N2 and suppresses the competing oxygen evolution reaction, while the amorphous, La-enriched interior furnishes active sites for N≡N bond cleavage. This spatial decoupling of capture and activation achieves a record Faradaic efficiency of 40.4%, and it offers a viable route toward decentralized, renewable-driven fertilizer production.