Defining stability in metal-organic frameworks through rigorous characterization

MOFs are promising porous materials for energy, environmental, and industrial applications but only if they are stable under relevant conditions. Smoljan et al. present a tutorial-style perspective outlining rigorous, multi-technique characterization protocols for four major stability classes: thermal, chemical, mechanical, and radiation. Demonstrated across seven well-known MOFs, these protocols provide a practical roadmap toward standardized, comparable stability reporting.

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Protein olympiadanes

Mechanically interlocked proteins represent an emerging frontier in chemical topology and protein engineering. Here, we demonstrate the direct synthesis of protein olympiadanes—higher-order catenanes inspired by the Olympic rings—within living cells using a modular assembly strategy. The platform enables the construction of multiple constitutional isomers and produces exceptionally stable architectures. By providing a modular route to increasingly complex protein topologies, this work establishes a foundation for the programmable construction of mechanically interlocked proteins.

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Reaction: The art of autonomous chemistry

Agentic artificial intelligence (AI) promises self-driving laboratories (SDLs) capable of autonomous reasoning, yet general-purpose synthetic chemistry remains overwhelmingly manual. Automation still stumbles on ordinary tasks, remains costly and inaccessible, and offers too little relief to justify adoption. Moreover, poor FAIR (findable, accessible, interoperable, reusable) data practices leave AI models ill trained for chemistry. The authors call for democratized, modular hardware; rigorous FAIR data collection; and a Slurm-like workload manager distributing experiments across mature SDLs—freeing chemists to conceive questions rather than run columns.

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Reaction: Electrochemistry needs agentic AI that explains as well as optimizes

Self-driving laboratories can accelerate electrochemical discovery, but optimization alone is not enough. We argue that agentic artificial intelligence should recognize when objectives, models, or measurements are inadequate; explain anomalous results; propose competing hypotheses; and design discriminating experiments. But even with these capabilities, human scientists remain essential in identifying meaningful questions, evaluating explanations, setting research priorities, and ensuring accountability.

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Molybdenum doping enhances backbonding at neighboring iron centers in iron-sulfur clusters

Why is the Mo nitrogenase more adept at N2 reduction than its alternative nitrogenase counterparts (V and Fe-only)? To investigate this question, we undertook a comparative structural and spectroscopic analysis of synthetic [MoFe3S4] and [Fe4S4] clusters. We found differences in how the clusters distribute electron density, with the iron centers in the [MoFe3S4] clusters being better at backbonding to weakly π-acidic ligands. Such differences may account for the greater efficiency of the Mo nitrogenase.

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The influence of heterometals on dinitrogen binding at synthetic iron-sulfur clusters

Of the three nitrogenase isozymes (Mo, V, and Fe-only), the Mo nitrogenase shows the highest selectivity for N2 vs. H+ reduction. Here, we study the reduction chemistry of a series of synthetic [MFe3S4] clusters and find that only those that contain large auxiliary metals bind N2 at Fe. These results support an electronic role for “heterometals” featuring diffuse orbitals in facilitating N2 binding at neighboring Fe sites.

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Catalyst: When self-driving labs begin to reason

Self-driving laboratories (SDLs) are evolving from automated experimental engines into reasoning scientific partners. In agentic SDLs, artificial intelligence (AI) agents coordinate perception, planning, experimentation, analysis, and reflection across the research cycle. By making metadecisions, including what to measure, which models to trust, when to ask humans, and how to revise hypotheses, agentic SDLs move beyond closed-loop optimization toward adaptive, context-aware scientific discovery. This Catalysis article discusses how reasoning agents can expand autonomy, accelerate learning, and reshape scientific practice.

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Reaction: Navigating the path to reasoning laboratories

The convergence of agentic artificial intelligence (AI) and self-driving laboratories promises to move autonomous science beyond closed-loop optimization toward deliberate scientific reasoning. But this transition will not be a single leap. We argue that it runs through semi-autonomous laboratories, where AI agents and human scientists share cognitive and physical workloads. The more consequential question is not when full autonomy arrives but what we optimize for along the way and whether we build systems that narrow science or expand its scope.

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Reaction: Building trust infrastructure for agentic experimental science beyond fragile eloquence

Agentic self-driving laboratories are transforming artificial intelligence (AI) from a mere experimental optimizer into a collaborator that hypothesizes, reasons, and adapts. To avoid becoming an “eloquent layer over brittle automation,” we must advocate for explainable reasoning, digital safety twins to counter the “curse of rarity,” safety-critic agents, verifiable agent-to-agent identity, and institutional governance. As autonomy expands, scientists shift from experimenters to stewards, a role sustained only by robust technical safeguards and a shared culture of safety.

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Phosphate group-assisted interfacial proton diffusion facilitates direct ethylene electro-oxidation to ethylene glycol

We report that interfacial proton accumulation is the key limitation on the Faradaic efficiency (FE) of direct ethylene oxidation to ethylene glycol at industrially relevant current densities. Thus, a phytic acid-modified AgPd (AgPd-PA) electrocatalyst is designed to facilitate the diffusion of interfacial protons and accelerate the formation of ∗OH. This strategy achieves a record FE of 40.8% and a yield rate of 758.6 μmol h−1 at 100 mA cm−2 for ethylene glycol synthesis.

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Reaction: Self-driving labs need models of the chemical world

Self-driving laboratories are moving from automated execution to scientific reasoning. This reaction argues that the next step requires experimentally grounded models of the chemical world. Such models connect laboratory actions, latent chemical states, observations, uncertainty, and updates. They allow agents to choose experiments that test beliefs and improve metrics. Building them will require machine-executable protocols, multimodal measurements, provenance, transferable representations, and human judgment so that autonomous laboratories can accumulate chemical understanding across instruments, campaigns, and sites over time more reliably.

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Organopotassium for selective synthesis: Potassium-mediated anti-borylfunctionalization of alkynes

Organopotassium compounds are highly reactive organometallic species whose poor solubility and stability have long limited their synthetic applications. This study reports the potassium-mediated anti-selective difunctionalization of alkynes via reductive borylpotassiation. Reduction of alkyne with a potassium reductant in the presence of reduction-resistant trialkoxyborane results in anti-diboration. Performing the reductive borylpotassiation in flow microreactors enables the unsymmetrical borylfunctionalization of alkynes in an anti-fashion. These distinctive anti-selective difunctionalization reactions afford synthetically valuable multi-substituted alkenes, such as tamoxifen, with excellent regio- and stereoselectivity.

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High-entropy-inspired multi-principal single-atom materials

Multi-principal single-atom materials (MPSAMs) are inspired by the compositional complexity of high-entropy materials and the site-specific control of single-atom catalysis. This perspective conceptualizes key terminology, examines how high-entropy principles shape atomically dispersed designs, and critically assesses strategies to control atomic arrangements. The discussion explores how MPSAMs support cooperative functions across multiple metal sites within a confined space, enabling reactivity and selectivity unattainable with conventional SAMs. Challenges and future outlooks for entropy-informed catalyst design are further outlined.

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An isolable nitrene radical anion as a nucleophilic open-shell nitrogen synthon

Nitrenes are well-known reactive intermediates used to form a variety of nitrogen-containing molecules, but their reduced radical anions have remained inaccessible under ambient temperature. Here, a persistent nitrene can be converted into an isolable radical anion that features a non-Aufbau electronic configuration. This species acts as a nucleophilic nitrogen radical that forms new N–Se, N–Si, and N–C bonds under mild conditions.

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Single-chain-water ultrafast transport in COF membrane for dual desalination and devolatilization

Obtaining clean water requires removing both salt and harmful volatiles—a dual challenge where conventional membranes fall short. This study engineers a synthetic membrane with tailored nanoscale channels that overcome this limitation. It achieves high rejection of salt and volatiles while permitting fast water flow. This is enabled by a unique phenomenon where water molecules line up in a single file to move rapidly through the sub-nanometer pores.

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High-performance superphane membranes for sustainable flow batteries

Superphane cages construct precision-engineered subnanometer channels in membranes, enabling Grotthuss-driven rapid proton conduction and size-exclusion selectivity. This design simultaneously suppresses water migration via confined supramolecular interactions, which results in a record-low capacity decay of 0.008% per cycle in acidic flow batteries.

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Direct conversion of N2 and CH4 to valuable N-containing compounds via a plasma-activated catalytic process

Direct co-conversion of N2 and CH4 into alkylamines and NH3 is achieved under mild conditions via a non-thermal plasma-activated catalytic process over a Ni/SiAlO catalyst. The plasma-catalysis synergy not only facilitates the activation of reactants by increasing the mean electron energy but also enables catalyst-regulated N–C and N–H coupling of adsorbed intermediates with plasma-derived reactive species. This one-step process bypasses the energy-intensive Haber-Bosch and amination cascade processes, offering a sustainable synthetic route under mild conditions.

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Foam-to-foam recycling of non-isocyanate polyurethane foams via complete revalorization of depolymerization products

This work introduces a chemical recycling route that converts CO2-based non-isocyanate polyurethane (NIPU) foams back into cyclic carbonate building blocks (re-5CC) for direct re-foaming. A stepwise one-pot process combines foam deconstruction and re-functionalization, reusing all major depolymerization products while avoiding intermediate purification and reducing waste. The produced re-5CCs enable second-generation foams with up to 100% recycled carbonate source, advancing practical foam-to-foam recycling for NIPU foams.

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Advances in polymer chemistry enabled by transition metal catalysis

Transition metal catalysis has played a central role in driving advances in polymer chemistry. In this perspective, we present case studies where catalytic reactions initially developed for small-molecule substrates were subsequently used for the synthesis or modification of polymers. Applications in the preparation of functional materials and in the degradation, recycling, or upcycling of plastics are described.

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Sequential Zn2+-H+ storage in a 2D conductive metal-organic framework for advanced aqueous zinc-ion battery

The conductive 2D MOF Cu3(HHTATP)2 addresses H+-induced side reactions in acidic aqueous zinc-ion batteries by enabling voltage-separated sequential Zn2+ and H+ storage. Its multi-site redox chemistry, including reversible H+-mediated amine/imine conversion at pendant amines, suppresses LDH-related interference while affording high capacity, rapid ion diffusion, and excellent rate capability.

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Germanium ligand redox cooperativity: A key to ambiphilicity and switchable two- and four-electron transfer

This work shows that a main-group compound can be designed to engage in multielectron transfer chemistry often associated with transition metals. By pairing germanium with a redox-active ligand, the molecule can direct either two- or four-electron pathways and display both electron-donating and electron-accepting behavior at one site. This design offers a simple principle for building more versatile, earth-abundant systems for oxygen activation and related transformations in main-group chemistry.

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Actinide-actinide bonding visualized by Hirshfeld atom refinement

Covalency in chemical bonding is a well-established concept, but few methods experimentally measure covalency. X-ray charge density determination could be the most powerful method for visualizing chemical bonding, but its stringent requirements have prevented routine implementation. Hirshfeld atom refinement (HAR) has emerged as a more accessible approach for experimentally visualizing covalency, and here it is applied to two extreme test cases of trithorium clusters containing multi-center thorium-thorium bonding. We demonstrate excellent experimental-computational agreement, paving the way to the routine use of HAR visualization of chemical bonding.

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Visible light steers carbonylation utilizing carbon monoxide toward diversification and practicalization

This review summarizes recent research progress on carbonylation under visible-light reaction systems. The contents are categorized according to methods for activating substrates. Ultimately, this review aims to inspire the design of novel visible-light-induced carbonylation and promote the advancement of CO utilization in sustainable organic synthesis.

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Triggering expeditious Zn2+ DMSO-bridged deposition through high-entropy, H2O-depleted hydrogel electrolyte for wide-temperature zinc batteries

The single H2O solvent system is the primary factor limiting Zn2+ deposition kinetics and a battery's operating temperature window. We reconstructed the Zn2+ solvation structure and H2O molecule hydrogen-bonding network by designing a multi-solvent system, thereby achieving expeditious deposition kinetics and broad temperature-range operation for the battery. Our work provides new insights into durable and high-rate aqueous batteries capable of operating in real-world, thermally fluctuating environments.

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Light-induced diluted CO2 capture and photoreduction

We synthesized a series of stable metal-organic frameworks (MOFs) composed by [FeIII2MII(μ3-O)] (abbreviated as Fe2MO) clusters, denoted as USTC-12-Fe2M (M = Mn, Co, Ni), for photocatalytic CO2 reduction in a 15% CO2 atmosphere. Remarkably, USTC-12-Fe2Mn exhibits an ultrahigh CO2-to-CO conversion rate, reaching ∼16.1 mmolCO·gcatalyst−1·h−1 with 95% CO selectivity and an apparent quantum efficiency of 2.66% under visible-light irradiation. Experimental results reveal that Fe is the real active site driving photocatalytic CO2 reduction, with the divalent metal in the cluster modulating the Fe electronic state. In situ experiments demonstrate that CO2 molecules can be readily captured by the μ3-O atom and pre-activated on Fe2MO clusters to form ∗c-CO32− intermediates under light irradiation, enabling CO2 photoreduction at low CO2 concentrations.

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Copper-catalyzed doubly enantioconvergent radical C(sp3)–P cross-coupling for the construction of P- and P,C-stereogenic centers

Liu and colleagues report a copper-catalyzed enantioconvergent radical C(sp³)–P cross-coupling of racemic secondary phosphine oxides and H-phosphinates with alkyl bromides in order to enable the efficient synthesis of P-stereogenic phosphorus compounds. The same catalytic platform further enables the doubly enantioconvergent construction of vicinal P,C-stereocenters from racemic H-phosphinates and racemic secondary benzyl bromides. This method provides a general and practical approach to phosphorus-centered chirality and may inspire the development of related strategies for other heteroatom-centered stereogenic systems.

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Interface engineering of Fe-based multifunctional catalysts for selective CO2 hydrogenation to C3+ alcohols

Highly selective hydrogenation of CO2 into higher alcohols with three or more carbon atoms remains challenging due to inherent difficulties in regulating C–C coupling of reaction intermediates. Combined experimental and theoretical investigations reveal that a well-tailored K-modified ZnZrOx–Fe5C2 interface optimizes alkyl-oxygenate coupling, enabling efficient higher alcohol synthesis with a record-high C3+ alcohol yield and excellent long-term stability. This work demonstrates great practical potential for producing value-added chemicals via CO2 hydrogenation.

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