A Ru-functionalized carbonized TS-1 zeolite (Ru@TS@C) enhances charge transfer and photogenerated carrier separation, enabling photo-assisted near-neutral Zinc–air batteries with exceptional 4e− selectivity (74% lower overpotential, 218 versus 844 mV at 0.2 mA cm−2 under light) and reversibility. Extended to Li–O2 systems, it delivers superior rate capability and cycling stability, establishing zeolite-based photoactive cathodes for advanced metal–air batteries.

Neutral aqueous Zn−air batteries (ZABs), while promising for extended lifespans and recyclability compared to alkaline systems, are hindered by sluggish kinetics that limit energy efficiency and power output. Here, we report an effective approach to construct a photo-assisted near-neutral ZAB based on a photo-responsive titanium silicalite-1 zeolite (TS-1). The incorporation of Ru active centers into the 3D porous architecture of TS@C (Ru@TS@C), which exhibits remarkably enhanced electronic conduction, creates interconnected conductive pathways. This unique design facilitates rapid charge transfer across the 3D network, enabling exceptional reaction kinetics, and improved separation efficiency of photogenerated electron–hole pairs. Synergistic experimental and theoretical analyses reveal a photoinduced charge transfer mechanism in the conductive zeolite, where light-driven Ru-mediated electron exchange with oxygen adsorbates accelerates 4e−-dominant oxygen reduction reaction (ORR) kinetics. Consequently, the Ru@TS@C-based photo-assisted ZAB exhibits exceptional 4e− selectivity and reversibility, achieving a low overpotential of 218 mV at 0.2 mA cm−2 under illumination (74% reduction compared to dark conditions). Extended to Li–O2 batteries, this multifunctional architecture demonstrates superior rate capability and cycling stability (>150 cycles). This work pioneers the use of photoactive zeolites in metal–air batteries and establishes a universal framework for engineering photo-responsive interfaces to overcome intrinsic kinetic limitations in sustainable energy systems.

Amphiphilic linear block copolymers self-assemble into inverse photonic glass beads with ull visible-range coloration. The porous morphology and reactive design enable post-synthetic control over pore size and wall thickness, paving the way toward scalable, chemically programmable pigmentss for next-generation optical systems.

Structurally colored colloids, or photonic pigments, offer a sustainable alternative to conventional dyes, yet existing systems are constrained by limited morphologies and complex synthesis. In particular, achieving angle-independent color typically relies on disordered inverse architectures formed from synthetically demanding bottlebrush block copolymers (BCPs), hindering scalability and functional diversity. Here, we report a conceptually distinct strategy to assemble three-dimensional inverse photonic glass microparticles using amphiphilic linear BCPs (poly(styrene-block-4-vinylpyridine), PS-b-P4VP) via an emulsion-templated process. By employing trans-1,2-dichloroethylene to promote interfacial water infiltration, nanoscale aqueous domains form within the organic phase and direct short-range-ordered pore structures. Evaporative solidification arrests these structures into porous photonic beads with angle-independent color. Systematic control of surfactant alkyl chain length and BCP molecular weight enables precise tuning of pore size, shell thickness, and visible-range optical output. Furthermore, post-chemical modification via quaternization of P4VP provides an orthogonal chemical handle to modulate interfacial instability and photonic behavior. This work expands the self-assembly capabilities of linear BCPs and establishes a modular, scalable platform for producing structurally and chemically programmable photonic pigments.

The translation of new dynamic covalent thioorthoester chemistry into crosslinked metal scavengers and porous sulfur-rich lithium battery cathodes is highlighted as an example how the integration of new principles in supramolecular chemistry can open new directions to approach questions of significance in science and society.

Supramolecular chemistry promises that insights into contact between molecules will open up new directions to approach significant questions in science and society. In this spirit, Kraus et al. report the translation of fundamentally new dynamic covalent thioorthoester chemistry into metal-scavenging porous network materials and sulfur-rich, leakage-free cathode composites in lithium batteries (https://doi.org/10.1002/anov.70000).

Novel phenylamine-substituted 1,2-dioxetanes were developed as efficient luminophores with enhanced performance in aqueous media requiring no additives compared to phenoxy-1,2-dioxetanes. The amino-substituted benzoates yielded over 200-fold higher emission than phenoxy analogs. The NHMe-Diox probe showed rapid chemiexcitation, high quantum yield, and enabled sensitive β-galactosidase detection in bacteria with 130-fold improved sensitivity.

Chemiluminescence offers distinct advantages for bioimaging and sensing, notably by eliminating the need for external light excitation and minimizing background interference. While the original phenoxy-1,2-dioxetanes have served as the cornerstone of chemiluminescent probe design, their efficiency is significantly compromised in aqueous environments. In this study, we report the development and evaluation of phenylamine-substituted 1,2-dioxetanes as a new class of luminophores with markedly enhanced performance under physiological conditions. By incorporating amino-substituted benzoates, we achieved over 200-fold higher chemiluminescent emission compared to a conventional phenoxy analog. Among these, the mono-methylated probe NHMe-Diox exhibited improved properties, including fast chemiexcitation kinetics, high quantum yield, and excellent signal-to-noise ratios, enabling sensitive detection of β-galactosidase activity in vitro and in live bacterial cells. These phenylamine-1,2-dioxetane probes function as single-component probes without requiring surfactants or enhancers, offering a significant advance in the design of chemiluminescent tools for biological and diagnostic applications. Significantly, probe NHMe-Diox demonstrated a 130-fold greater sensitivity compared to its phenoxy-1,2-dioxetane analog for the detection of E. coli bacterial cells.

A metallaphotoredox platform enables asymmetric incorporation of amine fragments onto quaternary carbons via photocatalytic generation of α-amino alkyl radicals and nickel-catalyzed coupling with alkene-tethered aryl bromides. The method accesses challenging stereocenters with high enantioselectivity and functional group tolerance, expanding the toolbox for constructing diverse amine-containing quaternary carbons in drug discovery.

The enantioselective construction of quaternary carbon stereocenters bearing amine functionalities represents a significant challenge in organic synthesis despite their prevalence in pharmaceutically active compounds. Herein, we report a versatile metallaphotoredox platform for the asymmetric incorporation of amine fragments onto quaternary carbons via coupling of alkene-tethered aryl bromides with readily available α-silylamines. This transformation proceeds under mild conditions without requiring organometallic reagents or stoichiometric reductants. Mechanistically, photocatalytic generation of α-amino alkyl radicals enables their enantioselective coupling with chiral quaternary carbon-containing alkyl nickel species. The method delivers exceptional enantioselectivity and exhibits broad functional group tolerance, providing access to a diverse array of complex drug-like molecules bearing amine-functionalized quaternary stereocenters. Mechanistic investigations revealed the intermediacy of cage-escaped, stereodefined quaternary carbon-containing radicals, which guided the development of complementary asymmetric hydrocyclization and difluoroalkenylation protocols. Our unified platform expands the chemical space of three-dimensional quaternary carbon scaffolds, demonstrating the potential of metallaphotoredox catalysis in addressing longstanding synthetic challenges.

Here, we show that 3D electron diffraction (3D ED) is an effective technique to observe structural transformations in porous metal-organic polyhedra (MOPs), as well as for obtaining the structure of the activated phases of these materials. A MOP-to-coordination polymer transition is revealed, and explains the reduction in cooperative gas uptake by the material as it is mechanically downsized via ball milling.

Porous metal-organic polyhedra (MOPs) have strong covalent and coordinate bonds that define the intrinsic pore of the cage. The intermolecular interactions between cages tend to be weaker, such that they rearrange during the solvent exchange process preceding gas sorption measurements. The reduction in crystal size that this often causes limits the availability of structural data that could enable understanding of observed gas uptake. Herein, we use 3D electron diffraction (ED) to resolve this problem, and apply this technique to a MOP-based material that shows cooperative gas capture. 3D ED structure solution reveals both that the MOPs rearrange to form porous 1D polymers, and that these polymers are retained in the activated phase. Molecular simulations using these data suggest gas uptake is facilitated by rotation of functional groups appended to the backbone of the polymers in conjunction with structural expansion as gas is accommodated. Mechanical downsizing of the material leads to the loss of cooperative gas uptake, but a level of porosity is retained, attributed to the conservation of the 1D polymer structure. This work underscores the potential of 3D ED for probing structural transformations in functional supramolecular materials.

A versatile DNAzyme-amplified protease-sensing (DP) platform was developed through the ingenious integration of positively charged peptides and DNAzyme (Dz) for the rapid detection of various target proteases. This platform exhibits superior sensitivity compared to traditional nonamplified protease-sensing (PP) platforms, thereby enabling the accurate diagnosis of SARS-CoV-2 and reliable classification of colorectal cancer (CRC).

Peptide-based biosensors are widely used for in vitro detection of protease activity but often suffer from the limited sensitivity, poor accuracy, and incompatibility with point-of-care testing (POCT) devices. Herein, we developed a versatile deoxyribozyme (DNAzyme)-amplified protease-sensing (DP) platform that integrates the positively charged oligopeptides with a negatively charged DNAzyme biocatalyst for highly-sensitive protease detection. The system leverages the electrostatic peptide–DNAzyme interactions to inhibit DNAzyme catalytic activity, which is reactivated upon the protease-triggered peptide hydrolysis, thus enabling an efficient signal amplification via the successive cleavage of DNAzyme substrate. Compared to conventional peptide-based sensing platform, our DP system offers an enhanced sensitivity and signal-to-noise ratio and is highly modular for detecting various clinically relevant proteases through a simple replacement of the peptide blocker. By introducing a dual-enzyme recognition mechanism, we developed a dual-protease-triggered DP platform for enabling the accurate detection of SARS-CoV-2 proteases in saliva. We also applied the DP platform to differentiate between normal and cancerous colon cells and tissues by detecting colorectal cancer (CRC)-associated proteases. Overall, this work introduces a universal and scalable biosensing strategy for activity-based protease detection with potential applications in both infectious disease diagnostics and cancer classification, advancing the field of DNAzyme-based POCT technologies.

By combining gas-phase rotational spectroscopy and quantum chemistry calculations, we explore how a prototype molecular photoswitch is affected by microhydration. This study unveils the theory-breaking structural features of camphorquinone oxime, the concerted dynamics of the surrounding water network, and how the oxime subunit actively steers the geometry of the first hydration shell.

With the goal of manipulating (bio)chemical processes, photoswitches emerge as important assets in molecular nanotechnology. To guide synthetic strategies toward increasingly more efficient systems, conformational dynamics studies performed with atomic rigor are in demand, particularly if this information can be extracted with control over the size of a perturbing solvation layer. Here, we use jet-cooled rotational spectroscopy and quantum chemistry calculations to unravel the structure and micro-hydration dynamics of a prototype photoswitch. Camphorquinone-oxime has a switching function enabled by the oxime moiety, and a chiral subspace generated by camphor, ensuring motion directionality. Although it may seem a relatively simple molecule, several popular levels of theory disagree on the energy ordering of the two switch states. We find that the oxime moiety integrates cooperatively into linear water chains captured for the dimer and trimer topologies, as well as into more exotic three-dimensional structures created for the complex with the water tetramer. Evidence for concerted hydration dynamics emerges from a comparison between theory and experimental isotopic information. We evaluate the balance of intermolecular forces at play during the hydration network build up and discuss how a flexible first solvation layer may affect the switching dynamics of this class of systems.

Polythiophene-based nanoparticles with abundant morphologies are efficiently fabricated by template synthesis strategy, which involves the fabrication of morphology precursors via PISA technique and their further oxidative polymerization. This strategy creates opportunities to obtain conjugated polymer nanoparticles with tunable morphologies and offers a powerful approach for large-scale fabrication to expand their application in future.

Polythiophene-based nanoparticles (PTNPs), a prominent class of conjugated polymer nanoparticles (CPNs) with remarkable optical and electronic properties, have gained significant attention in applications such as electronics and bioimaging. However, current methods in generating PTNPs have run into obstacles including low variety of morphologies, poor reproducibility, and low preparation efficiency, restricting their further application. In this study, we report a facile and efficient fabrication strategy based on template synthesis method. This method combines polymerization-induced self-assembly (PISA) for the preparation of morphology precursors (PTN-templates) with subsequent oxidative polymerization to realize the construction of PTNPs. By systematically regulating composition, charge characteristics of hydrophilic segments, and solids content of the polymerization mixtures during RAFT-mediated PISA, a wide variety of PTN-templates with various morphologies were obtained. The successful synthesis of PTNPs with representative morphologies was confirmed through morphology retention, the formation of polythiophene chains, and the observed red shift in UV-vis absorption and fluorescence emission spectra. In summary, we have established important guidelines for efficient fabrication of PTNPs with diverse morphologies, which opens up new avenues for the synthesis of next-generation conjugated polymer nanomaterials and offers the opportunity for the large-scale preparation of conjugated polymer nanomaterials.

The t 2g-to-π* π-backbonding and the unique open nanotube architecture are successfully constructed in the carbon quantum dot-functionalized trimetallic spinel nanotubes (FCNO@CQDs) for the chlorine evolution reaction (CER). The optimized FCNO@CQDs requires only 174 mV overpotential to achieve a current density of 0.5 A cm−2, maintaining for 240 h without obvious degradation, and displays selectivity up to 99.0%.

Facing the massive energy consumption of over 200 TWh y−1 of chlor-alkali industry, developing high-activity and durable non-precious CER (chlorine evolution reaction) catalysts is urgently needed to address the high overpotentials and suppress the dissolution high-valance metal species. Herein, a carbon quantum dots functionalized trimetallic Fe/Co/Ni spinel oxide nanotube architecture (FCNO@CQDs) is constructed, featuring t 2g-to-π* π-backbonding for dramatically enhanced CER activity and stability. The reverse electron flow from Co d-obritals to the vacant CQDs’ π* orbitals can upshift the d-band center for enhanced intermediate adsorption, while stabilizing high-valent Co centers via increased bond order. Meanwhile, the open nanotube architecture facilitates rapid mass transfer and efficient Cl2 desorption, validated by fluid dynamics simulations and in situ microscopic analysis. Electrochemically, FCNO@CQDs achieves an ultralow overpotential of 174 mV at 500 mA cm−2 and exceptional selectivity of 98.8%–99.7% across a broad potential range, outperforming commercial Ru/Ir-based dimensionally stable anodes (DSA). Mechanistic studies reveal a dynamic transition from the Volmer–Heyrovský pathway to a hybrid Volmer–Heyrovský and Tafel mechanism under high Cl* coverage (θ Cl ∼72%), enabling rapid kinetics. By bridging molecular orbital theory with nanoscale architecture design, FCNO@CQDs provides a valuable strategy for optimizing cost-effective, high-performance CER catalysts.

The high-pressure strategy achieves the significant enhancement of lithium-ion conductivity by 2 orders of magnitude and the disappearance of grain boundary resistance in polyoxometalate Li3PW12O40 electrolyte via an irreversible phase transition from Keggin to bronze structure.

Solid-state lithium-ion batteries have raised considerable attention due to their great potential for the development of new energy storage devices with high energy density and safety. However, enhancing ion conductivity in solid-state electrolytes stands as a pivotal challenge for the large-scale commercialization of next-generation lithium-ion batteries. Here, a high-pressure strategy is reported to achieve the significant enhancement of lithium-ion conductivity by 2 orders of magnitude and the disappearance of grain boundary resistance in polyoxometalate Li3PW12O40 electrolyte via an irreversible phase transition from Keggin to bronze structure. High-pressure in situ structure analyses revealed that the Keggin structure started to transform into the bronze structure at 18.0 GPa, and completed the transition around 34.0 GPa. Detailed density functional theory (DFT) calculations indicated that the bronze structure captured under pressure had a lower migration barrier (0.051 eV) and activation energy (0.091 eV) than the Keggin structure, which was mainly attributed to the corner-sharing WO6 octahedra and PO4 tetrahedra forming tunnels that can accommodate Li+ ions and provide transport channels. These results not only offer novel insights into optimizing the ion conductivity of solid-state electrolytes but also hold promise for developing new electrolyte materials under pressure.

An integrated CO2 reduction and methanol oxidation system employing CuBi cathode and NiCo anode enables efficient cogeneration of formic acid. The electron-rich Bi sites accelerate HCOO* formation, while low-coordination Co atoms enhance methanol oxidation. The coupled system delivers total Faradaic efficiencies of 189%–192% across 2.0–2.8 V, achieving sustainable and energy-efficient FA production.

The coupling of electrocatalytic CO2 reduction (ECR) and methanol oxidation reaction (MOR) presents a promising strategy for simultaneous cogeneration of formic acid (FA) at both cathode and anode. However, sluggish kinetics, low selectivity and efficiency hinder practical application. Herein, we demonstrate an integrated ECR||MOR system employing CuBi cathode and NiCo anode for energy-efficient FA cogeneration. The CuBi alloy achieves high Faradaic efficiencies (FE > 90%) for FA generation over an extensive potential range (>400 mV), attributed to the accelerated formation of HCOO* intermediates in facilitating FA production. Meanwhile, the NiCo alloy reached a remarkable FE of 97.5% for FA generation at 1.4 V versus reversible hydrogen electrode, benefiting from rapid HCOO* intermediate formation that effectively mitigates CO toxicity. This unique system delivered a current density of 10 mA cm−2 at a voltage of 2.07 V, representing a substantial reduction of 320 mV compared to water electrolysis. Across a wide operational voltage window (2.0–2.8 V), the system consistently delivered total Faradaic efficiencies ranging between 189% and 192%, alongside exceptional FA production capacities surpassing 400 g kWh−1, which significantly outperformed traditional methods (∼220 g kWh−1). This work provides an efficient pathway for low-energy CO2 utilization and sustainable FA production.

A SiO2-induced loose CeO2 as an effective capture for Pt atoms. The abundant surface O vacancies in the loose CeO2 trigger significant electron transfer from Pt to CeO2, therefore stabilizing Pt atoms under high temperature for reverse-water gas shift reaction with a record CO production rate of 7672.7 molCO molPt −1 h−1.

Pt-based catalysts exhibit extraordinary potential in reverse-water gas shift (RWGS) reactions, but often fail to possess a high reaction rate and high durability at the same time under high temperature. Herein, we designed a SiO2-induced loose CeO2 as an effective capture for Pt atoms. The abundant surface O vacancies in the loose CeO2 can trigger significant electron transfer from Pt to CeO2 and play a crucial role in stabilizing Pt atoms, therefore, largely improving its thermal stability. The as-synthesized Pt-aCeO2@SiO2 catalyst possesses a record CO production rate of 7672.7 molCO molPt −1 h−1 with CO selectivity > 97% at 400 °C surpass most of the reported Pt-based catalysts. More importantly, over 90% of the initial activity of the catalyst remains after 200 h constant operation at 400 °C, verifying the improved durability of Pt atoms under high temperature. Our investigation proposes a method of inducing the formation of defect-rich active supports through amorphous substrates, providing new thinking for designing atomic catalysts with good stability under high temperatures.

We report that the selectively catalytic effect of the electrode leads to the formation of a bilayer-SEI: the inner region is dominated with inorganic components derived from preferential reduction of anions, while the outer layer consists of elastic polymers triggered by the nucleophilic electrode surface. This bilayer-SEI can mitigate electrons leakage and improve mechanical robustness, thus ensure long-term stability.

Controlling the electrode-electrolyte interfacial behavior is crucial for achieving a high-quality solid electrolyte interphase (SEI) and ensuring sustainable battery performance. Here, we propose a selective catalysis strategy to stabilize antimony atom-cluster (SbSA-AC) anode/electrolyte interface for robust potassium-ion batteries (PIBs). Specifically, the electrode featuring SbSA-AC in porous carbon (SbSA-AC/PC) as “electrocatalyst” unduly catalyzes the reduction of the dimethyl ether-based electrolyte, resulting in loose SEI layer and rapid capacity decay. While in triethyl phosphate-based electrolyte, the SbSA-AC/PC selectively catalyzes the preferential decomposition of anions and the polymerization of solvent molecules, leading to a bilayer SEI with inner inorganic-rich components and an outer elastic polyphosphate layer, which improve the interface stability and electrochemical performance. Thus, the SbSA-AC/PC maintains a long-term stability over 12 months and demonstrates long-cycling stability over 4000 cycles with a capacity retention of 96%. This research establishes a correlation between electrode/electrolyte interactions and SEI characteristics, providing a new insight for advanced interface engineering in high-performance PIBs and beyond.

A new N-heterocyclic carbene (NHC) stabilized lithium complex is introduced as a thermally stable atomic layer deposition (ALD) precursor. It features a rare mononuclear structure, suitable volatility, and a low melting point of 55 °C. ALD trials yielded lithium silicate films. This study opens new directions for NHC-ligand chemistry in thin-film deposition applications.

Lithium is the core material of modern battery technologies and fabricating the lithium-containing materials with atomic layer deposition (ALD) confers significant benefits in control of film composition and thickness. In this work, a new mononuclear N-heterocyclic carbene (NHC) stabilized lithium complex, [Li(tBuNHC)(hmds)], is introduced as a promising precursor for ALD of lithium-containing thin films. Structural characterization is performed, comparing density functional theory (DFT) and single-crystal X-ray diffraction (SC-XRD), confirming a rare mononuclear structure. Favorable thermal properties for ALD applications are evidenced by thermogravimetric analysis (TGA). The compound exhibits a low melting point, clean evaporation, and its volatility parameters are encouraging compared to other lithium precursors. ALD trials using [Li(tBuNHC)(hmds)] with ozone demonstrate its effectiveness in depositing LiSi x O y films. The ALD process exhibits a saturated growth per cycle (GPC) of 0.95 Å. Compositional analysis using Rutherford backscattering spectrometry/nuclear reaction analysis (RBS/NRA), X-ray photoelectron spectrometry (XPS), and glow discharge optical emission spectrometry (GD-OES), confirms the presence of lithium and silicon in the expected ratios. This work not only presents a new ALD precursor but also contributes to the understanding of lithium chemistry, offering insights into the intriguing coordination chemistry and thermal behavior of lithium complexes stabilized by NHC ligands.

“I am most proud of my group when they are the strongest critics of their own data… My favorite podcast is PodCAT (I do not listen to podcasts except this one because I know the people in it)…”

Find out more about Tibor Szilvási in his Introducing… Profile.

The spatially separated efficient CO conversion and high-purity H2 production are realized by electrochemistry-accelerated water–gas shift reaction (WGSR) with IrN4–RhN4 dual sites single atom catalysts (IrRh–NC) in high-temperature polymer–electrolyte–membrane electrolyzer. The electrolyzer achieves superior CO catalytic performance (424 mA cm−2 at 0.4 V) and high purity (99.9%) H2 production (3.2 ml min−1), surpassing the performance of particle catalysts.

The water–gas shift reaction (WGSR) is crucial to the hydrogen economy, which is hampered by the harsh conditions and complicated purification process. In this work, the spatially separated efficient CO conversion and high-purity H2 production are realized by electrochemistry-accelerated water–gas shift reaction (WGSR) with IrN4–RhN4 dual sites single atom catalysts (IrRh–NC) in high-temperature polymer–electrolyte–membrane electrolyzer. In this reaction, the Ir single atoms in the catalysts can rapidly dissociate H2O at an extremely low potential to supply abundant *OH, which ensures the *OH groups bind to the spontaneously adsorbed *CO on neighboring Rh sites to further accelerate CO conversion. What's more, the elevated temperatures (120–300 °C) maintain water in the gaseous state during the reaction, thus greatly facilitating mass transfer of the reactants CO and H2O within the reactor. Employing IrRh–NC as the anodic catalyst, the electrolyzer achieves superior CO catalytic performance (424 mA cm−2 at 0.4 V) and high purity (99.9%) H2 production (3.2 ml min−1), surpassing the performance of particle catalysts. This work illuminates the tantalizing possibility for sustainable hydrogen economic development.

The modification of redox-active isoindigo molecule on Ag catalyst promotes CO2 electro-reduction to CO in acid. Collective impacts are revealed by combining theoretical, in situ spectroscopic and catalytic analyses. Lewis acid-base complexation is the dominant contributor with the assistance of intramolecular hydrogen-bond and interfacial water network effects, augmenting stabilization and activation of CO2-bound intermediates.

The electrocatalytic carbon dioxide (CO2) reduction is challenged by the parasitic hydrogen evolution reaction (HER) especially in acidic media. Here, we elaborate that redox-active isoindigo, acting as a multifunctional co-catalyst, can pre-activate CO2-bound intermediates and suppress HER upon the synergistic effects of Lewis acid-base adduct formation, intramolecular hydrogen-bond interaction, and interfacial water structure modulation. Modifying a silver catalyst with isoindigo substantially decreases the energy barrier for CO2-to-*COOH conversion, which is regarded as the potential-limiting step of carbon monoxide production. Accordingly, superior catalytic performances are obtained at pH 2, where Faradaic efficiencies surpass 99% at industrial-relevant current densities. Moreover, we find that assembling an additional polyamine-coated layer in front of gas flow channels improves CO2 transport to the catalyst layer, optimizing the trade-off of conversion and selectivity at low flow rates.

A in-situ polymerized interface is successfully constructed between solid polymer electrolytes and electrodes. Al(OTf)3 in the electrolyte initiates 1,3-dioxolane polymerization to lower interfacial impedance, while fluoroethylene carbonate-derived CEI suppresses sulfurized polyacrylonitrile’s shuttle effect. This enables the Li-S battery to retain 90% capacity after 200 cycles at 0.5C.

Lithium-sulfur batteries have been regarded as a promising candidate for next-generation energy storage systems owing to their high energy density and low cost. Sulfurized polyacrylonitrile (SPAN) as a cathode material has received wide interest due to the solid-solid conversion mechanism, while the Li-SPAN cell performance has been limited by the notorious issue of lithium metal anode. Developing solid-state electrolytes for lithium-sulfur batteries with favorable electrode-electrolyte compatibility is urgently desired. Herein, we demonstrate a dual-interface optimization strategy through in-situ polymerization interface construction, which synergistically enhances interfacial compatibility between the solid polymer electrolyte (SPE) and both the lithium metal anode and SPAN cathode. The initiator pre-buried in the SPE triggers the in-situ polymerization of 1,3-dioxolane (DOL) at the interface, thereby greatly reducing the electrode/electrolyte interfacial impedance. Additionally, the released fluoroethylene carbonate (FEC) into the poly-DOL interface could further reduce the impedance and enhance the interface stability during cycling, simultaneously preventing the dissolution of polysulfides, owing to the inorganic-rich and dense cathode electrolyte interphase formed on SPAN. As a result, the Li-SPAN cell could operate more than 200 cycles at 0.5C with a capacity retention of 90%. We believe that this strategy provides prospects for the development of high-energy solid-state lithium-sulfur batteries.

This study explores the mechanistic investigation into an unusual reactivity of a thioether-ligated low-spin Fe(III)-alkylperoxide with cyclohexane–carboxaldehyde as a mimic of nonheme iron(II) enzyme intermediates and highlights that only efficient catalysis happens from a high-valent iron(IV)-oxo species.

Metalloenzymes activate molecular oxygen within their catalytic cycles to generate a reactive species capable of substrate transformation. In many iron-containing enzymes, it is a high-valent iron(IV)-oxo complex that is synthesized from an iron(III)-alkylperoxo intermediate, although direct observation and characterization of such species have remained elusive, leaving their mechanistic role uncertain. To address this gap in our understanding, we present here the synthesis, comprehensive characterization, and reactivity of a novel thioether-ligated iron(III)-alkylperoxo complex supported by the ligand 2-((2-(pyridin-2-yl)ethyl)thio)-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine. Characterization was done using UV–vis spectroscopy, resonance Raman spectroscopy, electron paramagnetic resonance spectroscopy, and electrospray ionization mass spectrometry. Reactivity studies reveal that this complex exhibits electrophilic oxidation of model substrates, including dimethylsulfide, triphenylphosphine, and cyclohexanecarboxaldehyde. Notably, the latter substrate reacts via the unusual aldehyde C─H bond abstraction leading to cyclohexanecarboxylic acid, which is explained by favorable aldehyde C─H abstraction transition states due to stabilizing interactions between the ligand framework and the substrate. Moreover, the reaction is initiated with a homolytic O─O bond cleavage in the iron(III)-alkylperoxo group that yields a reactive iron(IV)-oxo species that mediates substrate oxidation. To our knowledge, this work represents the first example of a mononuclear low-spin (S = ½) nonheme iron(III)-alkylperoxo complex displaying such unprecedented electrophilic reactivity.